The move has been anticipated since last week and will save the Saints $3.2 million against the salary cap. Colston, 32, was released with a failed physical designation, which may be tied to the chest injury that sidelined him for the final two games last season.
Colston called the Saints a "first class organization" and expressed his thanks to the franchise in a statement posted to his website.
"To everyone from the Benson family, the front office, coaches, and the training and equipment staff: It has been a pleasure to be part of a family with so many great people," Colston said.
On Tuesday, Saints coach Sean Payton said in a statement, "His production, consistency, toughness and work ethic were second to none. You always knew what you were going to get from Marques and that was everything that he had. All of the characteristics that Marques possess are what we look for in a New Orleans Saint. I thank Marques for all that he did for our team and wish him the best of luck."
Colston had a remarkable 10-year run in New Orleans after being drafted in the seventh round out of Hofstra in 2006. His 9,759 receiving yards and 72 touchdowns are both franchise records, and he helped lead the Saints to their first Super Bowl championship after the 2009 season.
"To my fellow players: thanks to each of you for sharing this journey with me, challenging me to grow as a player, and an individual," Colston said. "It's been an honor to work beside you, and as a team we achieved something that can never be duplicated -- the first Super Bowl victory for NOLA."
However, Colston became the Saints' No. 3 receiver last season, with career lows of 45 receptions, 520 yards and four touchdowns in 13 games played.
The Saints also released all-time great guard Jahri Evans -- another member of that 2006 draft class -- earlier this month. Those moves should put them nearly $10 million under the salary cap, with a contract extension for Drew Brees likely to provide even more cap savings at some point this offseason.