The 52-year-old from Toronto will direct the women's eight at the Summer Olympics next month, one of seven Canadian crews headed to London.
"It's a very experienced and seasoned team," Rowing Canada high performance director Peter Cookson said Thursday after the team was nominated. "We have a lot of former Olympians coming back or who have stayed with the program.
"For some of them, it's their second Olympics. For many of them, it's their third and for some it's their fourth."
Thompson-Willie is running out of fingers to count her Olympic experiences.
A member of the Canadian Olympic Hall of Fame, she was first named to the 1980 Games, which Canada boycotted. She went on to appear in the 1984, 1988, 1992, 1996, 2000 and 2008 Olympics.
"She is really a rock in that boat in terms of just keeping everything steady and balanced and going forward," said Cookson. "She's been a dream to have around in terms of getting this team prepared."
The five-foot-three 110-pounder is looking to become the first Canadian to win medals in five different Olympics.
Canada has qualified seven crews in the 14 Olympic events this time round.
"I think all of the boats that we have going in are really high-calibre crews," said Cookson. "And if we race to our potential, then we're going to come home with our fair share of the medals, if everyone does what we know they can do."
Four years ago in Beijing, Canadian rowers won a gold (men's eight), silver (coxless pairs) and two bronze (men's lightweight coxless fours and women's lightweight double sculls).
David Calder of Victoria and Scott Frandsen of Kelowna, B.C., won the silver four years ago and are back for more.
"They have been unbelievably great in terms of their preparation and getting themselves ready to go and compete," Cookson said of the pair. "They've been true leaders ... They demonstrate ever day a huge commitment to making this happen."
The 2012 Olympic regatta will be held at Dorney Lake, a rowing and flat-water canoeing centre set in 180 hectares of parkland near Windsor.