After graduating from FTII, Rao spent the next year visiting studios and meeting casting directors. In 2010, he got his big break when he was cast in Love Sex aur Dhokha, after responding to an ad that mentioned Dibakar Banerjee was looking for newcomers.Rao next signed Ekta Kapoor’s Ragini MMS where he played a negative role. Both Love Sex Aur Dhokha and Ragini MMS succeeded, and his performances in both films were appreciated. He also appeared in Bejoy Nambiar's Shaitan. Raja Sen of Rediff, while criticizing the film, singled out his performance as "reliably terrific"In 2012, Rao performed a series of small, but significant roles in films like Gangs of Wasseypur – Part 2, Chittagong and Talaash. Anurag Kashyap selected Rao for Gangs Of Wasseypur, after watching his performance in Love Sex aur Dhokha. For the role of Shamshad Alam, he visited Wasseypur to perfect his character and accent. However, his character's screen time was considerably reduced in the final script. Rao who was eager to work with Anurag Kashyap, went ahead with the movie anyway.[6] In the critically acclaimed Chittagong, he portrayed the role of freedom fighter, Lokenath Bal. In Talaash, he played the role of a junior officer to Aamir Khan's character. Rajeev Masand of CNN-IBN commented, "...it takes Rajkumar Yadav just one scene - in which he's merely a spectator with a single line of dialogue - to show what a good actor can bring even to a small part."