Rao, at present the chief executive of Allahabad Bank, will head the Delhi-based PNB till September 18, 2021, the government said in a notification issued late Tuesday.
Rao, a career banker, has 33 years of banking experience behind him.
He will replace Sunil Mehta in PNB, which is currently under a process of three-way amalgamation with Oriental Bank of Commerce (OBC) and United Bank of India.
Rao started his career as probationary officer in Bank of Maharashtra in 1985 and had also worked in Global Trust Bank before its merger with OBC. He also worked in Syndicate Bank as executive director.