Kate Richardson-Walsh and Helen Richardson-Walsh will compete at their fourth Olympics, while Crista Cullen and Alex Danson will be at their third.
Striker Lily Owsley, 21, who won hockey's rising star award last year, will make her Games debut.
Barry Middleton has been named in the GB men's squad for the fourth time.
The 16-strong squad also includes Nick Catlin, Dan Fox, Iain Lewers and Harry Martin, all of whom were part of the squad that finished fourth in London.
GB women, who won the EuroHockey Championships in London in August 2015, came fifth in the six-team Champions Trophy in London this month, while the men finished fourth.
The Rio Games run from 5 to 21 August.
Giselle Ansley, Sophie Bray, Crista Cullen, Alex Danson, Maddie Hinch, Hannah Macleod, Shona McCallin, Lily Owsley, Sam Quek, Helen Richardson-Walsh, Kate Richardson-Walsh, Susannah Townsend, Georgie Twigg, Laura Unsworth, Hollie Webb, Nicola White.
Reserves: Joanna Leigh, Eleanor Watton, Kirsty Mackay.
David Ames, Alastair Brogdon, Nicholas Catlin, David Condon, Adam Dixon, Daniel Fox, Mark Gleghorne, Michael Hoare, Ashley Jackson, Iain Lewers, Harry Martin, Barry Middleton, George Pinner, Ian Sloan, Samuel Ward, Henry Weir.
Reserves: James Bailey, Simon Mantell, Dan Shingles.

Kjell Lindgren played Amazing Grace on the pipes after recording a message about research scientist Victor Hurst, who was involved in astronaut training.
It is thought to be the first time that bagpipes have been played in space.
They were made for Mr Lindgren by McCallum Bagpipes at the company's factory in Kilmarnock, Ayrshire.
Kenny Macleod, who works at McCallum Bagpipes, told BBC Scotland the 42-year-old astronaut had got in touch two years ago to say he was going to the space station and wanted to play the pipes while he was there.
"He wondered if it was feasible to play bagpipes," he said.
"They're made of plastic - they're just easier to keep clean and to make sure they're not contaminated. They're also lighter."
In the video, Mr Lindgren is seen to give the pipes a punch before he starts playing. Mr Macleod said it was normal for pipers to massage the bag to get the air flowing, "but not quite as vigorously as that".
"The thing about bagpipes is that they're very difficult to play at high altitude because the air is that bit thinner. They're quite hard to blow so he's done well," he added.
There are six astronauts currently in space on the 45th expedition to the International Space Centre.
In a video recorded in the last few days, Mr Lindgren said all of them had come into contact with Dr Hurst during their training and were "shocked and saddened" to hear about his death.
Dr Hurst worked for US engineering company Wyle Science as a research scientist and instructor. He died suddenly in October, aged 48.
Nasa flight engineer Mr Lindgren said: "He always had a quick smile, a kind word. I don't know if anyone was more enthusiastic and professional about being involved in human space flight."
Eight of the women's team who won a bronze medal at London 2012 have been named in the Great Britain hockey squad for this summer's Olympics in Rio.
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A US astronaut has played a set of Scottish-made bagpipes on the International Space Station to pay tribute to a colleague who died.