He entered active politics and became member of the Babhalgaon Village Panchayat from 1974 to 1979 and its Sarpanch (village chief) from 1974 to 1976. He was a member of Osmanabad Zilla Parishad and Deputy Chairman of Latur Taluka Panchayat Samiti (Latur District Panchayat Committee) from 1974 to 1980.
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He was Member of the Maharashtra Legislative Assembly from 1980 to 1995. During this period, as the Minister of State and the Cabinet Minister, Deshmukh handled departments such as Home, General Administration, Cooperation, Public Works, Transport, Legislative Affairs, Tourism, Agriculture, Animal Husbandry, Dairy Development Fisheries, Industry, Rural Development, Education, Technical Education, Sports and Youth Welfare,
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He took oath as the Chief Minister of Maharashtra on October 18, 1999. He held Chief Minister Office till 17 January 2003.
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He was re-elected to the State Legislative Assembly from Latur Constituency in the Elections held in October 2004.
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He has been a minister in various governments in Maharashtra from 1982 to 1995 holding portfolios of revenue, cooperation, agriculture, home, industries and education.
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He took oath as the Chief Minister of Maharashtra for the second time on November 1, 2004 and held the office till December 2, 2008.
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He was appointed Union Minister for Heavy Industries and Public Enterprises by Prime Minister Dr Manmohan Singh on 28th May 2009.
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He has visited Japan, Thailand, Philippines, Taiwan and Hong Kong in 1980, to study Cooperative Movement in Amsterdam, Netherland and Agricultural Development. He also visited West Germany, France, England, United States and Japan in 1981. As the Chief Minister of Maharashtra, he led an official delegation in May 2000, to U.S.A. and UK and visited New York, Los Angeles, San Jose, Washington and London to interact with the investors to bring investment to Maharashtra.
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He has founded the Manjra Charitable Trust which runs a number of colleges in Latur & Mumbai. Some of them are Manjara Ayurvedic College & Hospital, Latur, Rajiv Gandhi Institute of Technology at Versova, Andheri in Mumbai and Sushiladevi Deshmukh Vidyalaya at Airoli, Navi Mumbai.
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He has been elected unopposed as Vice President of the Mumbai Cricket Association (2009-2011), Election held on 10th July 2009.
