On December 18, 2012, Thibault was introduced as the new head coach & general manager of the Washington Mystics. He led a revival of the team, getting them to the playoffs and earning a win there for the first time since 2004. For his efforts, Thibault once again earned the Coach of the Year award, joining Van Chancellor as the only coaches to win the award three times.
Thibault served as an assistant coach for the USA National team in 2006, a team in transition. Lisa Leslie, who had led the team in scoring in the 2004 Olympics, the 2002 World Championships, the 2000 Olympics, the 1998 World Championships, and the 1996 Olympics was no longer on the team. Sheryl Swoopes was available but hampered by injuries, with Staley transitioning from player to coach. Newcomers Sue Bird, Candace Parker and Diana Taurasi picked up the slack, but it was a team in transition. As an additional challenge, some members of the squad were unable to join the team for practices due to WNBA commitments. The team started out strong, winning each of the six preliminary games, including the game against Russia. In the quarterfinals, the USA team beat Spain 90–56. The semifinal was a rematch against Russia, but this time the Russian team prevailed, 75–68. The USA faced Brazil in the bronze medal game, and won easily 99–59.