Other talent already in place includes Matt Vasgersian, Victor Rojas, Trenni Kusnierek, Hazel Mae and former Major Leaguers Al Leiter, Joe Magrane, Dan Plesac and Harold Reynolds.
"I'm excited to join my new team," Larkin said in the Network's statement. "It's great to be part of something from the development stages, and I'm looking forward to working with the group to build a great program."
MLB.com's Bill Ladson reported Larkin's intention to join the MLB Network on Monday. The 44-year-old Larkin spent four seasons as an assistant to Washington general manager Jim Bowden and at one point was offered the team's first-base coaching job, but declined because of family commitments and interests outside of baseball.
Larkin said he also had an opportunity to return to the Reds, but instead chose the MLB Network.
Larkin will be part of the first broadcast, which will go on the air at 6 p.m. ET on Jan. 1 with a live, one-hour Hot Stove studio show. Don Larsen's perfect game in the 1956 World Series will follow, airing for the first time since its original broadcast and featuring new commentary by Larsen and Yogi Berra.
The MLB Network is projected to launch in approximately 50 million cable and satellite homes, exceeding any other cable television launch by approximately 20 million. It will feature live games, original programming, highlights, classic games and coverage of baseball events.
Larkin is considered one of the best shortstops in Reds history, collecting 2,340 career hits with a lifetime batting average of .295. Larkin also won the National League Most Valuable Player Award in 1995 and three Gold Gloves.
He will bring his insight to a pair of the Network's key programs. MLB Tonight will air live on Monday-Saturday beginning at 6 p.m. ET until the final MLB game of the night ends, and will be based out of MLB Network's headquarters in Secaucus, N.J. The program will feature live look-ins of games in progress, updates, highlights, reporting and analysis.
Hot Stove will air during the offseason at 7 p.m. ET from Monday-Friday and will feature news, reports and analysis of the moves clubs are making and planning in preparation for the upcoming season.