Although he again split time between the two clubs the following season, by 2000, Vokoun established himself in the NHL, though he initially only saw limited action as the back-up to starter Mike Dunham.

In 2002, Dunham was traded to the New York Rangers for Marek Židlický, Tomáš Klouček and Rem Murray, effectively awarding Vokoun the starting job.

Vokoun's play was solid enough in 2003–04 to send him to the All-Star Game for the first time, and his goaltending was a major factor in the Predators' first-ever playoff berth that season.

In game 4 of that series, played in Nashville, Vokoun earned the first-ever playoff shutout in franchise history, stopping 41 Red Wing shots.

[1] During the 2004–05 NHL lockout, Vokoun played 19 regular season games for HIFK in the Finnish SM-liiga, posting a .940 save percentage.

He missed the team's remaining regular season games and the entire playoffs while he recovered by taking blood-thinning drugs and avoiding physical activity.

[2] Back-up goaltender Chris Mason took his place as the starter, but the Predators failed to advance in the playoffs, again losing in the quarter-finals.

[4] Vokoun's nine-year tenure in Nashville had him setting many of the Predators' goaltending records, all of which were overtaken by Pekka Rinne in the following decade.

With Washington resorting to youngster Braden Holtby as their starting goaltender, Vokoun was traded to the Pittsburgh Penguins on 4 June 2012 in exchange for a seventh-round pick in the 2012 NHL Entry Draft.

His first international experience came with the under-20 team at the 1996 World Junior Ice Hockey Championships, where the Czechs finished in fourth place.