The 32-year-old had been playing for the Aragua Tigers in the Venezuelan Winter League.
Venezuelan league president José Grasso Vecchio said on Twitter that the accident occurred on the Central Regional Highway outside Caracas.
Garcia, who originally signed with the Yankees in 1996, pitched 46 games for the Rangers in 2003 and was 1-2 with a 6.02 ERA. On June 16, 1999, García became the first starting pitcher in Staten Island Yankees history.
Besides pitching in the minor leagues and for the Rangers, García's career included stints in his home country as well as in Mexico.
He began his career at age 18 with the Tigres de Aragua of the Venezuelan Professional Baseball League during the 1997-1998 season. In 2008, García joined the Mexico City Red Devils of the Mexican League, where he started 14 games and went 4-5 with a 5.15 ERA and 44 strikeouts.
He pitched four games for the Rangers in 2004 but never returned to the majors.
"He was a good kid, he really was," former Rangers manager Buck Showalter said, according to MLB.com.
"He really cared. He was a good teammate, always had a smile on his face. He really tried hard and loved playing. He was pleasant, full of energy and always loved helping his team win."