Sharapova will bring her expertise on Russia to the Peacock Network's coverage, with the Olympic Games taking place in her hometown of Sochi.
"I'm thrilled to be joining the NBC family for [next] year's Olympic Games in my hometown of Sochi," she said.
The athlete continued: "The Olympic experience is unlike anything else, and as a past Olympian it means even more to me for the Games to be hosted in such a remarkable place.
"Sochi has such a rich history and culture, and I'm excited that it will now hold a place in so many athletes' hearts from all over the world."
Sharapova is among the most decorated modern professional tennis stars, having won a silver medal at the London Olympics and also both the French and US Open tournaments.
NBC has also enlisted gymnast Nastia Liukin and figure skater Johnny Weir to be part of its broadcast team for the Olympic Games.
NBC begins its Olympics coverage in February.