Ms Murmu, 64, was declared the candidate for the coming presidential election on Tuesday, after the Bharatiya Janata Party approved her choice in a meeting of the BJP-led National Democratic Alliance.
If elected, Ms Murmu would replace incumbent President Ramnath Kovind and become the second woman to hold the top constitutional post. Pratibha Patil held the top job between 2007-2012.
Ms Murmu, from eastern Odisha state, belongs to the Adivasi community — a marginalised tribal group in the country.
She would also become the first president born after India’s independence in 1947.
Mr Modi said her administrative experience and “gubernatorial” tenure will make her a “great president” and her “compassionate” nature will benefit the country.
“Millions of people, especially those who have experienced poverty and faced hardships, derive great strength from the life of Smt Droupadi Murmu Ji. Her understanding of policy matters and compassionate nature will greatly benefit our country,” Mr Modi said in a tweet.
Formerly a teacher, Ms Murmu later served as a legislator and as a minister between 2000 and 2004 in the coalition government of Odisha state’s ruling Biju Janata Dal party and BJP.
She was also the first woman from the community to have served as the governor of neighbouring Jharkhand state.
Ms Murmu has been pitted against Yashwant Sinha, former BJP leader and a vocal critic of Mr Modi, chosen as the joint opposition candidate.
The presidential elections will be held on July 18 and the counting of votes will take place on July 21.
Her candidacy is likely to augment Mr Modi’s party’s image among tribal voters in the coming elections in states such as Gujarat, Madhya Pradesh, Rajasthan and Chhattisgarh, which have prominent tribal populations.
The states in total have 128 seats reserved for tribes but the BJP had won just 35 seats in the last assembly elections.