Love will join fellow tour veteran Jay Haas as part of Couples' staff for the biennial team competition, which pits a 12-man team from the United States against a line-up of international players from outside Europe.
This year's edition will be played from October 4-6 at Muirfield Village Golf Club in Dublin, Ohio, site of this week's Memorial Tournament.
"I'm really excited to have Davis as part of the team," Couples, 53, said in a statement. "He is one of my closest friends and his experience as a team member and Ryder Cup captain will be invaluable at Muirfield in October.
"I know his friendships and relationships with the players out on tour will also be a huge help to me leading into the Presidents Cup."
Love, who captained the U.S. team at last year's Ryder Cup where they lost to Europe by 14-1/2 points to 13-1/2, played in six Presidents Cups between 1994 and 2005, compiling a 16-8-5 record including a 5-2-1 mark in partnership with Couples.
"I'm so excited to help Freddie out as a captain's assistant," said Love, 49. "This is going to be an incredible venue for the event, and it will be fun to be back in the team room with the guys again so soon.
"I hope to play alongside potential U.S. team members a lot this year and help Fred out that way since I'm on tour more than he is. I'm just glad to be a part of the event."
Three-times Major winner Nick Price of Zimbabwe will captain the Internationals at Muirfield Village and has appointed compatriots Mark McNulty and Tony Johnstone and Japan's Shigeki Maruyama as his assistants.
The U.S. have established a virtual stranglehold on the Presidents Cup, winning the trophy at Royal Melbourne Golf Club in Australia in 2011 for the seventh time in nine editions.
The only success for the Internationals came in 1998 when the event was first staged in Melbourne. In 2003, the teams battled to a 17-17 draw in South Africa.