MLB Network would produce the game on behalf of Facebook and also distribute specially curated content in addition to each live game broadcast.
Facebook had tied up with MLB last year to air 20 of the league's games live.
The first broadcast will be the match between National League East rivals, the Philadelphia Phillies and New York Mets, on April 4.
As fans increasingly watch games online, social media companies have increased their focus on signing live-streaming sports deals.
Separately on Friday, Major League Soccer (MLS) announced a three-year deal with Twitter Inc to stream live matches, highlights and other content on the micro-blogging platform. Last year, MLS had partnered with Facebook to offer a similar suite of content.
(Reporting by Supantha Mukherjee and Uday Sampath in Bengaluru; Editing by Shounak Dasgupta)
