Group C has drawn tournament co-hosts Gabon against shock qualifiers Niger as well as North African rivals Morocco and Tunisia - who contested the 2004 Nations Cup final.
Until the last round of matches, the group will be based in the Gabonese capital Libreville.
Gabon will enter the most important competition in its football history on a high after the country won its first African title last month.
The Under-23 side won the Confederation of African Football's inaugural continental championship, qualifying for London 2012 - Gabon's first Olympic football tournament - at the same time.
Four of the side have made coach Gernot Rohr's senior squad for the Nations Cup, with captain Cedric Boussoughou joined by Remy Ebanega, Henri Ndong and Andre Biyogo Poko.
But the Panthers also boast plenty of experience with veteran striker Daniel Cousin, 34, up front alongside Nice striker Eric Mouloungui, 27, although the attack failed to impress in Gabon's last two warm-up games - both of which ended goalless.
The squad's stand-out player is St Etienne star Pierre-Emerick Aubameyang, 22, who can either play wide or up front and who has already bagged six league goals for his French side this season.
Unlike fellow co-hosts Equatorial Guinea, the Gabonese have participated in previous Nations Cups - making their debut in 1994 before recording their best display two years later when reaching the quarter-finals.
They have failed to reach the knock-out stages at their two tournaments since, although the Panthers did cause a stir when beating Cameroon 1-0 in their opening game at Angola 2010.
However, that was when Gabon last played a competitive match and under pressure to deliver from an expectant public, Rohr will hope to be right when saying that the confidence gained from winning the Under-23 title will spread through the squad.
Niger were THE shock qualifiers for this Nations Cup because few people, if any, expected them to finish above defending champions Egypt, 2010 World Cup hosts South Africa or Sierra Leone in their group.
Despite losing all their matches away from the blistering heat of their home stadium in Niamey, the Mena qualified for their maiden Nations Cup thanks to a 100% home record (and Bafana Bafana's embarrassing inability to understand the rules).
Harouna Doula's side shook up the African football hierarchy in dramatic style when beating Egypt - who had won the last three Nations Cups - 1-0 at home in October 2010 thanks to a goal from Moussa Maazou.
The Belgium-based striker is very much Niger's dangerman but a mix of bad luck and a temperamental nature have seen his club career plummet in recent times.
Aged just 23, he has played for six different clubs in four years - with high-profile sides CSKA Moscow, Monaco and Bordeaux amongst them - although he left the latter side after making derogatory comments about the club's fans.
At the other end, current Coton Sport goalkeeper Kassaly Daouda is a key player - as are Morocco-based striker Issoufou Dante and long-serving captain Idrissa Laouali.
Nonetheless, Niger's most important man in Malabo will be Doula, who was named the Confederation of African Football's Coach of the Year last month.
The former international has gained legendary status at home after qualifying for the finals and although the close bond and trust he enjoys with the players will count a great deal, his reputation as a fine tactician will be of more importance in a challenging group.
Since contesting - and losing - the 2004 final to then host nation Tunisia, Morocco's Nations Cup record has been one of major disappointment - suffering group stage exits in both 2006 and 2008, before failing to qualify for the 2010 finals altogether.
But like the Senegalese, the Atlas Lions have used their period in the international wilderness to come back as a far stronger unit - partly thanks to calling up talented dual nationals from the large Moroccan communities in Europe, such as Youssef El Arabi (France), Oussama Assaidi and Mbark Boussoufa (both Holland).
Belgian Eric Gerets took charge in October 2010 and a coach who has won league titles in three different countries has transformed an Atlas Lions side whose qualification campaign took off when thumping neighbours Algeria 4-0 in June.
And the former Marseille coach is so bullish about his side's strengths that he is targetting what would only be the country's second Nations Cup title - with the first coming way back in 1976.
With experienced goalkeeper Nadir Lamyaghri set to overcome injury, Morocco can boast a strong spine with the superb Mehdi Benatia (Udinese) at centre-back, Houssine Kharja (Fiorentina) in midfield and Marouane Chamakh (Arsenal) up front.
Throw talented players such as Mbark Boussoufa, Adel Taarabt and Youssef Al Arabi into the mix and you can understand why the Moroccans are outsiders for the trophy.
The Atlas Lions prepared for the finals in Marbella, Spain, training at the same camp that they used prior to the 2004 tournament - when they lost to North African rivals Tunisia in the final.
The pair meet at the Nations Cup for the first time since in the opening round of Group C games in Libreville, where vengeance will certainly be on the minds of many Moroccans.
With a minute left of African qualifying for the 2012 finals, Tunisia were facing an embarrassing exit from the competition - but they were reprieved when Chad scored the latest of equalisers to deny Malawi a place in the finals.
While it may not have been wholly convincing, the qualification represented a personal triumph for coach Sami Trabelsi who had taken charge in January 2011 with the team in dire straits and trailing the Malawians by two points.
Tunisia's 1998 World Cup captain earned his chance in March after leading his country to glory at the African Nations Championship in Sudan the month before.
This is a competition for home-based players, many of whom are now fixtures in the senior side - such as Aymen Abdennour and playmaker Oussama Darragui, 24, who was crowned the Africa-Based Player of 2011 by the Confederation of African Football.
However, striker Slama Kasdaoui, who top-scored at the African Nations Championship, will be a notable absentee since he has been plagued by injury after joining CS Sfaxien in August.
A more fundamental concern comes over the fitness of Issam Jemaa, who had been expected to be Tunisia's main goal threat at the finals (as he was in qualifying with six goals), but the Auxerre striker is set to miss the group stages with an ankle problem.
Trabelsi has said that his players' characters and minds have been fundamentally changed by the political revolution that overthrew former president Zine al-Abidine Ben Ali - stating that his players have been set free.
Whether this will be enough to win the Nations Cup away from Tunisia for the first time remains to be seen, with the Carthage Eagles' sole trip to a final on foreign soil coming when losing to host nation South Africa in 1996 - a game Trabelsi missed through suspension.