The voting began at 10 am at the Tilak Hall. After casting his vote, the chief minister told reporters that NDA candidate Ram Nath Kovind will win the election with a huge margin.
"This is matter of pride for the people of Uttar Pradesh, the son of the state is going to become the President", he said.
Both Mr Adityanath and Mr Maurya have not yet resigned from the Lok Sabha and are voters as MPs.
After the conclusion of voting at 5 pm, the ballot boxes will be sealed and sent to Delhi.
The NDA has fielded former Bihar Governor Kovind for the top constitutional post, while former Lok Sabha Speaker Meira Kumar is the joint opposition candidate.
The tenure of incumbent Pranab Mukherjee comes to an end on July 24.
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