Assistant Returning Officer Mukul Pandey told reporters that 96.94 per cent (761 out of 785) members eligible to cast vote have exercised their franchise till 3 pm.
NDA's M Venkaiah Naidu is pitted against opposition candidate Gopal Krishna Gandhi.
The strength of the electoral college comprising both elected and nominated MPs of Rajya Sabha and Lok Sabha is 790. There are two vacancies in each House.
One BJP Lok Sabha MP is barred from voting following a judicial pronouncement.
In fact, the prime minister was standing in queue even before the voting hall opened at 10 am.
Congress vice president Rahul Gandhi, his party MPs Jyotiraditya Scindia, Deepender Singh Hooda and Sushmita Dev also voted to elect the next vice president.
MPs are using special pens for marking their choice in the election which will conclude at 5 pm.
The counting of votes will commence after polling and the results will be declared by 7 pm, Election Commission officials said.
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