Stoney is a veteran of over 100 England caps and claims her top priority is to make sure the two Scottish players in the otherwise all-English squad, Kim Little and Ifeoma Dieke, fit straight in.
“I’ve got to take responsibility as captain,” she said.
“I’ve got to get the team together and I’ve already introduced myself to the two Scottish girls that I’m not really that familiar with.
“It starts on the field but I’ll be relishing my role off the field as well. I'll make sure everybody is as happy as possible and that we’ve got good team spirit going into the Games.”
Stoney was always likely to be handed the armband by coach Hope Powell, who gave her the same role with England following the retirement of her central defensive colleague Faye White earlier this year.
“I don’t think there’s a bigger honour or privilege than to lead the team out at an Olympics in a home country,” she added.
“I’m proud that Hope has trusted me with that honour. I’m looking forward to it and it’s a role I’ll relish.
“For me, it’s massive that Hope is coach as she knows me inside out, and I know the way she works and we’ve got a good relationship.
“It’s key going into the tournament. I think she’s a fantastic coach and manager and if anyone is going to lead us to success, it’s going to be her.”
Powell’s team will play a friendly against Sweden in Middlesbrough before opening up their Olympic campaign against New Zealand in Cardiff on June 25 - the very first Team GB athletes in action.
They then play Cameroon but it’s the group match against Brazil at Wembley on July 31 that is really exciting Powell and her team, as they will be the first British women’s team to play at the famous venue.
“I’m looking forward to playing in all the stadiums,” added Stoney.
“It’s the Olympics and every stadium is going to be fantastic, but to play at Wembley, it’s got to be a highlight.
“Obviously I’m an England player as well and to play at our national ground – can it get any better? Leading the girls out to victory would cap it off.”