She will have the task of trying to win back the Cup after the Americans lost a heartbreaker at Killeen Castle in Ireland in late September.
"It's an absolute honor to be selected as the 2013 U.S. Solheim Cup Team Captain," said Mallon. "I've participated in The Solheim Cup on nine occasions and each has been a proud moment for me, but to represent the United States as team captain definitely caps off my career. I look forward to working hard on getting the Cup back in U.S. hands."
Mallon, 48, played on eight American teams and amassed a 13-9-7 record. She collected 16.5 points in her Solheim Cup career and served as one of Beth Daniel's assistant captains in 2009.
An owner of 18 LPGA Tour victories, including four major championships, Mallon essentially retired during the 2010 season. Her last win came in 2004, the same year she fired a 65 on Sunday at the U.S. Women's Open, the lowest closing round in tournament history, to come from behind and win.
Mallon and Juli Inkster were the heavy favorites to be named to the post. Inkster played in her ninth Solheim Cup last year and is the leading point earner for the American side with 18.5. Mallon's 16.5 ranks second.
Inkster, 51, was a playing assistant for Rosie Jones at Killeen Castle and went 0-2-1. She halved her singles match against Laura Davies on Sunday and has 31 LPGA Tour victories with seven majors.
Mallon's U.S. team will try to reclaim the Solheim Cup at Colorado Golf Club.
Europe has not named its captain for that competition.