He is the first non-footballer in the history of the league to have become a brand ambassador.
Rohit comes on board following a series of major initiatives by La Liga in India since 2017.
The current ICC World No. 2, is the only batsman in the history of the game to have scored three double hundreds in the 50-overs format including a world record 264.
"I am truly delighted to be associated with La Liga. It's encouraging to see the Spanish giant have made inroads into the Indian football ecosystem through their grassroots programme," Rohit said.
"Personally, I see this as an interesting journey for me into the beautiful game with La Liga. I look forward eagerly to connecting with the football fans in India."
Jose Antonio Cachaza, managing director, La Liga India said, "India is a very important market for La Liga from a global perspective, we came here in 2017 to get a better understanding of the pulse of the nation.
"Over the past two years, and after several ground-breaking initiatives, it is obvious that India has a huge appetite for football. Rohit Sharma is the perfect example of this, in spite of being the most renowned face in Indian cricket right now, he is also an ardent football and La Liga fan.