Rao was born in September 1950 in Nanjing, Jiangsu, and graduated from University of Science and Technology of China in 1977.
He received his master's degree from Graduate School of Chinese Academy of Sciences in 1982, and PhD in biophysics from University of Melbourne in 1989.
He subsequently worked as a postdoctoral researcher in David Stuart laboratory in Oxford University.
In 1997, he returned to China and established the Structural Biology Laboratory in Tsinghua University.
He became the director of Institute of Biophysics, Chinese Academy of Sciences in 2003, and the president of Nankai University in 2006.