Dikembe Mutombo will cross the finish line for the group, which is trying to encourage kids to exercise.
Silver said Monday that he will run over the Verrazano-Narrows Bridge from Staten Island to Brooklyn then pass a baton to Chris Mullin, the Brooklyn native who starred at St. John's in Queens before a Hall of Fame NBA career.
Mullin, now an executive with the Sacramento Kings, will be followed by a long list of big-name players to cover the 26.2 miles.
Most also have local ties, including Bronx native and fellow Hall of Famer Nate "Tiny" Archibald; Knicks greats Charles Oakley, Bernard King and Allan Houston; the Nets' Darryl Dawkins; Brooklyn native Sam Perkins; and New York City high school legends Felipe Lopez and Albert King.
Also running is Jason Collins, who made history last season with the Nets as the first openly gay player in the four major North American pro sports leagues.
WNBA stars Swin Cash, Teresa Edwards, Ruth Riley and Katie Smith are on the relay along with players-turned-NBA TV analysts Greg Anthony and Steve Smith.
Rounding out the group are executives from the league, Knicks and Nets and broadcaster Mike Breen.
Each celebrity will be joined on his or her one-mile leg with a local student who takes part in marathon organizer New York Road Runners' youth programs. Silver will run alongside Lauren Pitarresi, a 14 year-old from Staten Island, "who I'm concerned is going to smoke me," he joked.
Silver is an avid runner who has twice completed the NYC Marathon, finishing in just under four hours in both 2002 and 2010. He competed in track and cross country — and not basketball — in high school in Rye, New York, where he was a quarter- and half-miler.
The 52-year-old Silver hasn't been running as much since he became commissioner in February. He still gets in four or five workouts a week, often taking two laps around the reservoir in Central Park for just over three miles.
He's not in good enough shape to do the full race Sunday, though it's a strange sensation as a marathoner to stop after only a few miles.
"I felt awkward running only a leg of the marathon and not the entire marathon, having remembered some famous New York stories of people who started and didn't necessarily finish," Silver said.
Plans for the relay began in the early spring. New York is home to this season's NBA All-Star weekend, with events at the Nets' Brooklyn arena and the game at Madison Square Garden.
The league is seeking to reach a half-million youngsters in the five boroughs through fitness programs in conjunction with hosting the festivities.
Silver will start just after Wave 1 on Sunday. He needs to be ready to leave his home on Manhattan's West Side at 6 a.m. to get to Staten Island, though he said he's "negotiating" a later pick-up.
Other participants will gather at a hotel in Manhattan or another in Brooklyn to be ferried to their baton-passing points, which will take place at mile-markers.
Twenty-seven vehicles will be required to get everybody to the proper places, with co-ordination from the New York Police Department to ensure they can be transported through the crowded streets.
Marathon officials expect the relay to take more than five hours.