The 30-year-old forward spent his first seven NHL seasons with Anaheim, helping the Mighty Ducks reach the Stanley Cup finals in 2003. Then he joined up with former teammate Teemu Selanne, and the pair signed free agent deals with Colorado for the 2003-04 season.
Terms weren't immediately available, but Kariya reportedly signed for two years and $9 million.
But Kariya had career lows with 11 goals and 36 points in an injury-plagued season that limited him to just 51 games.
Kariya missed 31 of the first 38 games because of a sprained wrist, and got into only one playoff game after he sprained his ankle in the Avalanche's last game of the regular season.
In 10 NHL seasons, Kariya has 311 goals and 705 points in 657 games.
"We are proud and excited to bring one of the National Hockey League's most dominant scorers over the past decade to Nashville," Predators general manager David Poile said. "Paul Kariya is a dynamic skater and playmaker and a perfect fit for our hockey club. This sends a strong message to our fans that the Nashville Predators are prepared to compete at the highest level."
They are one of the smaller-market teams that figured to benefit from the league's new $39-million salary cap.
Kariya, a seven-time All-Star, has recorded over 100 points twice, gone over 30 goals six times, and has averaged 1.073 points per game for his career.