The Prime Minister's Office cleared the appointment today, a day on which Naidu assumed charge as the 15th vice president of the country.
Rao, a 1979 batch IAS officer of Andhra Pradesh cadre, retired from service as special chief secretary last year.
He held several important posts in Andhra Pradesh and later served the UNESCO.
N Yuvaraj, AP cadre IAS officer of 2006 batch, will be the private secretary to Naidu, official sources told PTI in New Delhi.
Yuvaraj was till now PS to Venkaiah Naidu when he was the information and broadcasting minister.
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