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The election has coincided with the first day of Parliament's Monsoon session. Droupadi Murmu, 64, was a strong contender for the country's highest office before the 2017 presidential elections before Bihar Governor Ram Nath Kovind, a Dalit, was named as the government's choice for the post.
The NDA choice of Ms Murmu - a tribal woman from Odisha and a former Jharkhand Governor - is seen as a calculated move, drawing the support not only of Jharkhand's ruling Jharkhand Mukti Morcha, but also Odisha's Naveen Patnaik, seen as a fence-sitter.
Ms Murmu has also been assured of support by Bihar Chief Minister Nitish Kumar, who lately is seldom on the same page as ally BJP.
Both factions of the Shiv Sena - the split of which and the subsequent collapse of Maharashtra government dominated headlines for weeks - are also expected to support Ms Murmu.
While the Eknath Shinde faction, allied with the BJP, was supporting the NDA candidate, the faction led by Uddhav Thackeray is also supporting her.
The Thackeray faction, which was supporting Opposition candidate Yashwant Sinha, decided to switch after 16 MPs met Uddhav Thackeray and suggested that they should vote for Ms Murmu. Mr Sinha has claimed that Mr Thackeray has been arm-twisted into supporting Ms Murmu.
The opposition settled on Mr Sinha - a former Union Minister in the Atal Bihari Vajpayee government who later joined Trinamool Congress - after three proposed candidates said no.
National Congress chief Sharad Pawar, former Governor Gopal Krishna Gandhi and former Jammu and Kashmir Chief Minister Farooq Abdullah had all declined, citing various reasons.
The President is elected by the members of the Electoral College, comprising elected members of both houses of Parliament and legislative assemblies of all states as well as the National Capital Territory of Delhi and the Union Territory of Puducherry.
No party whip can be issued for the voting, and the MPs and MLAs can vote as they please. The counting of votes will be held on July 21 and the new President will take oath on July 25, under the schedule announced by the Election Commission.
