Anil Ambani, the head of the Reliance ADAG group, walked into a polling booth (for the Lok Sabha elections) in the tony Cuffe Parade locality, not far from his residence at the 'Sea Wind' tower at 0715 hours.
Full coverage: Lok Sabha elections 2014
Godrej chairman Adi Godrej, among the most respected corporate chieftains, also exercised his right to franchise in the morning hours.
However, mortgage lender HDFC's chairman Deepak Parekh was reportedly not able to vote as his name did not figure in the voters' list.
A source familiar with the development said Parekh went to the polling centre in South Mumbai around 8.30 am where he has been normally voting for decades and did not find his name in the list.
Among others who voted were State Bank of India's chairman Arundhati Bhattacharya, who cast her vote in the Malabar Hill locality, where her official residence is located.
N Chandrasekaran, who heads the country's largest software exporter Tata Consultancy Services, also voted in Worli early morning.
The vice chairman and chief executive of HDFC, Keki Mistry, exercised his right to franchise in south Mumbai along with his family.
Former banker and Aam Aadmi Party nominee from South Mumbai, Meera Sanyal also voted before going out in her constituency to oversee polling process.
Ajit Gulabchand, the chairman of infrastructure major HCC and a resident of Nariman Point in South Mumbai, also voted early.
Most of the companies have declared holiday today in order to encourage staff to vote. All the financial markets, including the equity bourses, money markets and commodity bourses, are shut today due to Lok Sabha polls.
Others who are expected to exercise their franchise later during the day include RPG's Harsh Goenka and Reliance Industries' Mukesh Ambani.