Rao, who was 84, breathed his last at a private hospital in south Delhi, his daughter-in-law and senior advocate Mahalakshmi Pavani said.
"He had a massive heart attack when we were near Moolchand flyover. We immediately took him to the hospital where he passed away," she said.
The cremation will be held tomorrow at 4 pm at Lodhi crematorium here.
Rao had appeared in several landmark cases including Babri Masjid demolition case and had opposed capitation fees in educational institutions.
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Rao, a Padma Bhushan awardee, was selected as jurist member of the selection committee of the Lokpal in 2014 after President of India's approval.
An LL.B. And LL.M. From Osmania University, Hyderabad, Rao started his career teaching law in Delhi University in 1961.
He was enrolled as an Advocate by the Bar Council of Delhi in 1967 and thereafter started practice in the Supreme Court.
He was elected President of the Supreme Court Bar Association in 1991.