He then went to Fresno State, where he led the Bulldogs to a Western Athletic Conference title in 1999 and set the NCAA record for career lowest percentage of passes intercepted.

[1] After such a small amount of play time, he would not be seen on the field again until the 2003 season, where he would make a name for himself as one of the National Football League's more talented backup quarterbacks.

In 2004, he became only the fourth quarterback in NFL history—along with Dan Marino, Dan Fouts, and Phil Simms—to pass for over 400 yards in two consecutive games,[2] a feat that was also accomplished in 2008 by New England Patriots quarterback Matt Cassel, in 2011 by Tom Brady and Cam Newton, in 2018 by Ryan Fitzpatrick, and in 2022 by Joe Burrow.

In late August 2006, coach Jeff Fisher announced that the Titans intended to sign Kerry Collins to compete with Volek for the starting quarterback job.

Many critics state that Volek took full advantage of his chances to become the starting quarterback, pointing towards the reasonably good preseason that the Titans had.

During the AFC Divisional Playoff game against the Indianapolis Colts on January 13, 2008, Volek replaced the injured Philip Rivers and led a fourth-quarter comeback over the defending champions.