2004 Olympic Games: finished 12th among 12 teams
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He is a former member of the Angola national basketball team, and competed for Angola at the 2004 Summer Olympics, 2005 African Championship, 2006 Lusophony Games and 2006 FIBA World Championship.
Biyombo, who was born in Lubumbashi, was discovered by the former Jordanian and Angolan and current Portuguese national team head coach, Mário Palma, at the age of 16 at a youth tournament in Yemen.
Over the years, the national team has included several players who have competed in the U.S. National Basketball Association, including former Charlotte Bobcats center DeSagana Diop, and is considered to be, along with those of Nigeria and Angola, a top African side.