From 1979 to 1983, Smt. Murmu served as a Junior Assistant in the Irrigation and Power Department, Government of Odisha. Later, she served as an honorary teacher at Sri Aurobindo Integral Education Centre, Rairangpur, from 1994 to 1997.
In 2000, Smt. Murmu was elected from the Rairangpur constituency as a Member of the Legislative Assembly of Odisha and continued to hold the post till 2009, serving two terms. During this period, she served as Minister of State (Independent Charge), Department of Commerce and Transport in the Government of Odisha from March 6, 2000 to August 6, 2002 and as Minister of State (Independent Charge), Department of Fisheries and Animal Resources Development, Government of Odisha from August 6, 2002 to May 16, 2004. In both assignments, she introduced innovative initiatives and people-oriented measures.
Shrimati Murmu studied elementary education at the local primary school in Uparbeda. At age five, she moved to Bhubaneswar for higher studies. She completed secondary education from Girl's High School Unit-2, and graduated in B.A. from Rama Devi Women's College.
She was also appointed a Member of various Committees including House Committees and Standing Committees of the Odisha Legislative Assembly. She also chaired some of the Committees.
With her rich administrative experience and thanks to her efforts to spread education in tribal societies, she carved a special identity for herself. For her services as a legislator, she was awarded the Pandit Nilkanth Das – Best Legislator Award in 2007 by the Odisha Legislative Assembly.
Smt. Murmu was appointed the Governor of Jharkhand on 18 May, 2015. She was the first woman tribal Governor of a tribal-majority State, and she received wide appreciation for upholding the values of the Constitution and supporting the rights of the tribal communities. She introduced reforms in examination and recruitment processes of the State Universities.
In 1981, Smt. Murmu married (late) Shyam Charan Murmu , who was an officer in a bank. She has a daughter, Smt. Itishree Murmu, and son-in-law, Shri Ganesh Hembram.