The 33-year-old, who now plays for MLS side DC United, has not played for England in nearly two years.
Former Three Lions captain Rooney last played for England in November 2016 but will make his 120th and final appearance for his country against the United States.
This will serve as Rooney's proper farewell to honour his incredible career as an England player, while the hope from the FA is that it will also raise more than £500,000 for a number of children's charities, including the NSPCC.
The 33-year-old striker will be named in Gareth Southgate's squad for a charity fund-raising friendly against the US at Wembley on 15 November. "I would like to thank Gareth Southgate and the Football Association for inviting me back and helping to support my foundation in the process", Rooney said in a statement.
The game will serve as a final chance for Southgate to fine-tune ahead of England's Nations League crunch match with Croatia on Sunday November 18. "It's fitting the match will be against the U.S.".
The former England captain is second on the all-time list of appearances made for England and now six behind Peter Shilton's record of 125. I hope that whilst I am with the squad I can pass on some of my experience.
As an England player, Rooney has won 71 games, drawn 29 times and lost just 19 of his matches at worldwide level.
His 12 goals in 21 DC appearances set up a meeting with Columbus Crew, but Rooney missed from the spot in DC's penalty shoot-out defeat following a 2-2 draw.
The player's rich vein of form, alongside his popularity among England supporters and the feeling of progress made under Southgate, have helped the FA with the decision.