London 2012 gold medallist will be joined by bronze medallist and younger brother Jonny in the bid for gold on Copacabana Beach in August, while their support will come from fellow Leeds triathlete Gordon Benson.
In the women’s team, Vicky Holland will look to build on her first ITU Series titles in Cape Town and Edmonton last year as she takes part in her second Olympics, along with former world champions Non Stanford and Helen Jenkins.
Holland and Stanford share a house in Leeds having moved to the city to train at the high performance centre at the start of the Rio cycle.
The team was announced by the British Olympic Association at Leeds Civic Hall on Tuesday.
Alistair Brownlee saw off Spanish rival Javier Gomez to win in London with brother Jonny taking bronze - and all available form guides hint at a similar podium despite what Brownlee believes will be a “very different” course in Rio.
Brownlee said: “I think it’s fair to say things have got a bit closer over the last few years but I don’t think we’ve all performed to the best of our abilities and if that happens in Rio the podium will be the same.
“But I think it will be a good, hard race and a very different race in Rio. Even if the podium positions end up looking very much the same, I’m sure the race itself is going to be very different.”
While the Brownlees will count themselves among Britain’s best gold medal bets in Rio, there are also rising hopes among the fast-rising women’s team, not least in the form of 30-year-old Holland.
She said: “Four years ago I was in a very different position - I was part of the team in a supporting role for Helen but things have changed for me in the last two years.
“My move to Leeds has been the catalyst for things in my career and in Rio I’ve got far loftier ambitions than 26th place this time round.”
British Olympic Association Chef de Mission Mark England said: “I would like to congratulate these six athletes on securing Olympic selection for Rio 2016 and welcome them all onto Team GB.
“At London 2012 we won our first medals in triathlon and since then we have gone from strength to strength as a nation.
“As Olympic medallists both Alistair and Jonny bring an incredible pedigree to the team and Gordon’s European Games triumph in Baku last year means the men’s team is very strong.
“Non, Vicky and Helen have all tasted World Championships success and I’m sure will go into the Games in great form and full of confidence.”