Authorities said their auto went to the opposite side of the road while trying to avoid a sliding rock. Both played for the team Thursday.
Castillo played from 2004 to 2008 in the majors with the Pittsburgh Pirates, San Francisco Giants and Astros.
The 33-year-old Valbuena played in 149 games for the Cubs in 2014, compiling 16 home runs and a.776 OPS.
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"We are living through a awful tragedy", the Cardenales said on Twitter.
Valbuena played for the Angels the past two seasons.
Two other people, including Cardenales de Lara third baseman and former major league player Carlos Rivero, also were in the vehicle and survived the crash, police said. He hit.199 with a.253 on-base percentage, a.335 slugging percentage, nine homers and 33 RBIs in 96 games for Los Angeles this year.
Former infielders killed in crash while leaving game in Venezuela. He hit.226 with 114 home runs over 11 big league seasons with the Angels, Seattle, Cleveland, the Chicago Cubs and Houston. "Our thoughts and prayers are with their loved ones during this time of grief". He played this year for Tijuana in the Mexican League.