Volek attended Fresno State University and Clovis West High School in Fresno, California. He is regarded as one of the National Football League's more talented backup quarterbacks since the 2003 season. It was announced on December 17, 2004 that he would be the starting quarterback for the rest of the 2004-2005 season for the Titans, replacing the injured Steve McNair. McNair's injuries healed in time for the next season, and Volek backed him up again, starting 1 game. McNair was traded to the Baltimore Ravens during June 2006, allowing Volek the opportunity to truly earn the starting position. In late August 2006, after Volek had a reasonably good preseason, coach Jeff Fisher announced that the Titans intended to sign journeyman QB Kerry Collins to compete with Volek for the starting QB job. In turn, it has been reported that Volek took issue with this decision and immediately asked to be considered for a trade. On September 19, 2006, Volek was traded to the San Diego Chargers for a conditional sixth round pick in the 2007 NFL Draft after the Titans played the Chargers in their 2nd game.