Mr Murmu, 64, a Santhal — a marginal tribal community — was nominated by Indian Prime Minister Narendra Modi’s ruling Hindu nationalist party as its presidential candidate last month.
The 64-year-old was declared as a candidate for the election after India's Bharatiya Janata Party approved her running during a meeting with the National Democratic Alliance.
She will replace President Ramnath Kovind — whose tenure ends this week — and become the second woman to hold the post after Pratibha Patil, who served from 2007 to 2012.
More than 4,800 legislators and parliamentarians cast their votes on Monday to choose between Ms Murmu and Yashwant Sinha for the nation's top constitutional job.
Who is Droupadi Murmu and what is her background?
Ms Murmu is from the Santhal tribe in eastern Odisha state.
She was born to a village headman in Baidaposi in 1958. Before entering politics, she worked as a schoolteacher and later as a junior assistant in the irrigation department until 1983.
She was married to Shyam Charan Murmu and had two sons and a daughter. Both her sons and her husband are dead.
An arts graduate, Ms Murmu has spent nearly two decades in politics and social services.
Ms Murmu has won strong support from the BJP’s allies and if elected, she would be the first tribal member to hold the presidency and become the first president born after India’s independence in 1947.
How did she become involved in politics?
Ms Murmu was elected as a village councillor in 1997 and later served as the vice president for the BJP’s tribal wing.
She entered formal politics after becoming a junior minister, holding the portfolio of commerce and transport, in the BJP and Odisha state’s Biju Janata Dal coalition government in 2000.
She was chosen by the Odisha Assembly as the best legislator of the year in 2007.
She was appointed the first tribal governor of Jharkhand, a tribe-dominated state, in 2015.
Known for her accessibility and a down-to-earth attitude, she was described as a “compassionate and balanced” administrator in Jharkhand.
She was considered for president in 2017 but Ram Nath Kovind, a Dalit parliamentarian and governor of Bihar, made the cut as nominee.
What is the role of India's president?
As ceremonial head of state, the Indian president has few real powers and acts chiefly on the advice of the government.
But most political parties regard a candidate's election campaign as an opportunity to display their nationwide political strength, as well as symbolism.
Parties often nominate candidates from marginalised groups such as the Dalits — formerly known as untouchables — and from the lowest rung in the Hindu caste hierarchy, women and religious minorities.
Hundreds of national and state legislators will vote to elect the president for a term of five years, with the BJP commanding about 48 per cent of the share of the ballot.