Molina was originally signed as an undrafted free agent by the Chicago White Sox on January 3, 2000. He spent seven years in the minor leagues with the White Sox organization before making his major league debut on April 2, 2007, with the White Sox. He was on the White Sox' opening day roster due to backup catcher Toby Hall being placed on the disabled list. Molina sent down to the minors once Hall returned. During Molina's short one-and-a-half month tenure with the White Sox, he went 1-18 with one RBI. He got his first hit against the New York Yankees at U.S. Cellular Field. Shortly after, he was sent down to the minors.
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