Jiménez played with the senior Spain national team at the 2006 FIBA World Championship, where he won a gold medal. He also won the silver medal at the 2008 Summer Olympics, as Spain lost against Team USA in the gold medal game. After that Olympic competition, Jiménez announced his retirement from the Spain national team, after having been the captain of that group of players. He retired at the time as the Spanish player with the most medals won in international tournaments for the Spain national team.