Rao (63) was fighting against cancer for last two years. He is survived by his wife Renu and two sons Jayant and Arjun.
"Narayan Rao was an exceptional leader. He had unshakable integrity and his ability to make time to address the concerns of every person at NDTV," the company said in a statement.
Meanwhile, in a message on its website, NDTV co-founders Radhika and Prannoy Roy said that he was a towering personality in every way.
"He leaves a gigantic vacuum in our lives. We are forever grateful for his selfless leadership at NDTV and for his friendship, kindness and decency as a human being to all of us," said Radhika and Prannoy.
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Rao had joined NDTV as General Manager in January 1995, looking after human resources, administration and operations of the organisation.
He was invited to join the board of NDTV in 1998 and had been its Executive Director since then.
Rao was was appointed Group CEO in 2007 and Executive Vice Chairperson in August 2011.
In October 2016, he was reappointed for a second tenure as Group CEO of NDTV, in addition to his responsibilities as Executive Vice Chairperson.
He had held important positions as President of the News Broadcasters Association, member of the Indian Broadcasting Federation and Vice President of the Commonwealth Broadcasting Association.
Rao was also member of the Ficci Entertainment Committee and the CII National Committee on Media & Entertainment.