Rafael Nadal will open proceedings on Centre Court on Monday as he begins the defence of his Wimbledon title against American Michael Russell.
The ladies' match between Italian sixth seed Francesca Schiavone and Australian Jelena Dokic follows on the show court.
Britain's Andy Murray will be third on as he launches his campaign against Spaniard Daniel Gimeno-Traver.
With light rain forecast, the Centre Court - with its retractable roof - guarantees play from 1300 BST.
Three-time finalist Andy Roddick and Tomas Berdych, who lost to Nadal in last year's final, are both in action on Court One after ladies' number two seed Vera Zvonareva - last year's beaten finalist - starts proceedings against American Alison Riske, weather permitting.
Berdych, seeded six, plays Italian Filippo Volandri before Roddick, who lost to Roger Federer in the finals of 2004, 2005 and 2009, takes on German Andreas Beck.
With play due to start at 1200 BST on all other courts, five-time ladies champion Venus Williams takes on Akgul Amanmuradova of Uzbekistan in the first match on Court Two, which also features men's seeds Gael Monfils and Fernando Verdasco, and ladies' number four seed Victoria Azarenka.
Britain's Katie O'Brien opens proceedings on Court Three against Japan's Kimiko Date-Krumm, while Court 12 - as well as hosting a Balkans duel between big-serving Croat Ivo Karlovic and Serb Janko Tipsarevic - sees an all-British ladies contest between Anne Keothavong and Naomi Broady.
British men's number three Dan Cox, ranked 272, plays world number 35 Sergiy Stakhovsky of Ukraine in the third match on Court 14.
Warm and sunny weather presided throughout the Wimbledon fortnight last year, with the translucent Centre Court roof only required briefly to allow the completion of a late Novak Djokovic match with the structure's lighting system.
The first match to be played partly under cover was the 2009 match between Amelie Mauresmo and Dinara Safina, while Murray's epic against Stanislas Wawrinka on the same day was the first match to start and finish under the roof.
But this year, with rain also forecast for Wednesday and Thursday, could see plenty more players experiencing the conditions for the first time, including six-times champion Roger Federer.
The Swiss, who begins his quest for a record-equalling seventh title against Kazakh Mikhail Kukushkin on Tuesday, has played grass-court tennis under a roof before in Halle, Germany - but not in SW19.
"Wimbledon is a different centre court, so definitely it will take some getting used to in the beginning," he said. "It will be interesting to see. I honestly thought it was going to be a bit of a rainy Wimbledon this year. The spring was just too nice all over Europe it seems."
The Wimbledon roof has had mixed reviews from those who have played under it, some claiming the humidity is stifling, others saying the grass became slippery.
"It's more humid," explained Murray. "It slows the conditions down and the balls become heavier."
World number two Novak Djokovic, who opens against Frenchman Jeremy Chardy on Tuesday, added: "I think when the roof closes it's a bit slower and a bit more slippery. But at least I know approximately what it feels like."
Should it be raining 45 minutes before play is scheduled to start on Centre Court on Monday, the tournament referee is likely to hit the button and shut out the elements so the 125th championships can start on time.
The roof takes 10 minutes to close and enables play to re-start within 30 minutes.
Two-time champion Nadal, unbeaten at Wimbledon since the 2007 final after missing the 2009 event through injury, will take centre stage when the action gets under way, with 33-year-old American Russell likely to be his first victim.
The Spaniard is feeling refreshed after a short break at home in Majorca - including "two fantastic rounds of golf" - following his quarter-final defeat by Jo-Wilfried Tsonga at Queen's Club.
"I hadn't spent a weekend at home since the Davis Cup match against Belgium in February, so I needed it," he said. "I enjoyed it a lot. On Monday I started to practise. Tuesday, too. By Wednesday I was here practising in the afternoon.
"My inspiration comes every day. I love to play big matches. I love to play in big stadiums like here, historic stadiums like Wimbledon. Tomorrow I start by playing the first match of the tournament on Centre Court; for me it's a dream."