Beijing 2008 silver medallist David Florence will lead a British team of five slalom canoeists at London 2012.
Florence, 29, won two of the best-of-three selection races in the men's C1 (one-man canoe) category on the Olympic course at Lee Valley.
He has also earned a place in the two-man C2 boat alongside Richard Hounslow.
Hounslow beat Athens silver medallist Campbell Walsh to selection in the K1 one-man kayak, with Lizzie Neave winning the place in the women's K1.
Etienne Stott and Tim Baillie join Florence and Hounslow in the men's C2, in which Britain will be represented by two boats at the Olympics.
"It's awesome. A little project Richard and I started two years ago has succeeded already," Florence told BBC Sport. He and Hounslow began competing together in the C2 in late 2009.
"What an achievement. We're going to the Games and I'm so pleased.
"It hasn't sunk in - I'm going to the London Olympic Games and that's amazing. Amazing."
The preparations of British paddlers came to a head here in a series of straight race-offs to decide Olympic selection. A number of world-class athletes broke down in tears as years of work to reach a home Games evaporated in the space of minutes.
Five of the squad did enough to earn selection, some by mere fractions of a second.
Each nation is normally limited to one entry per category. However, because Hounslow and Florence both won their individual events as well as teaming up for the C2, a quirk in the qualifying rules means they gain a 'bonus' place in the C2 - having already qualified for the Games in their other events.
That hands their team-mates Baillie and Stott a C2 place at the Games regardless of which crew is victorious at these trials - the two have one win apiece going into Sunday's finale.
Every other selection battle was resolved with a day to spare as Neave, Florence and Hounslow posted decisive second race victories in their individual events.
"I think there was 0.4 seconds in it in the end," said Hounslow of his clash with Walsh for the men's K1 place.
"I honestly didn't think I'd done enough. Campbell was on a flyer but he got held up a bit at the end and it was enough for me to take it.
"I'm delighted, but I'm devastated for the guys who missed out as well. I know how hard it is."
Walsh said: "The Olympic spot was entirely my motivation for the year, the winter's training, when it's cold. I had no thoughts past this weekend.
"Richard's done fantastically well. You've got to win the races, and I didn't.
"I've not experienced this too much, I've generally been pretty successful and done what I wanted. It's a new experience to miss out on an Olympic spot when I was capable of getting it."
Neave, 24, celebrated her victory as fellow K1 paddler Fiona Pennie, who missed out, was led away disconsolate in the background. "It's a bit of a shock," said Neave. "I can't believe it yet and won't until it's written on paper.
"We've all been neck-and-neck all winter. The past couple of weeks have been quite stressful and the last couple of days, very stressful."
British slalom canoeists have struggled to progress beyond bronze medals on the world stage since the last Olympics, but Florence will be installed as GB's leading hope for the Olympics when the team selection is confirmed in 10 days' time.
"To have to do this, with all the crowd and excitement and a place at the Olympic Games to lose or win, is good preparation [for London 2012]," he said.