Mr Katare, 61, a senior Congress leader, is survived by his wife, two sons and a daughter.
He was suffering from lung cancer and undergoing treatment at the Hiranandani Hospital in Mumbai since April 18, Madhya Pradesh Congress spokesperson Pankaj Chaturvedi said.
Mr Katare had remained absent from the House due to his illness. Congress had nominated senior party legislator and former minister Bala Bachchan as the acting Leader of Opposition.
He was elected from Ater assembly constituency in Bhind district.
Mr Katare started his political career from a remote village called Manepura in Bhind district and was awarded the title of 'Best Youth Coordinator' for his dedication and work in Muzaffarpur district of Bihar.
He was appointed as General Secretary of Madhya Pradesh Youth Congress in 1985 and discharged his duties till 1990. In 1995, he was adjudged the 'Best Minister' in Madhya Pradesh.
He served as the Minister of State of Home and also as Minister for Food and Civil Supplies in the then chief minister Digvijay Singh's Cabinet.
Mr Katare was awarded the Best legislator in 2008 by former Lok Sabha Speaker Somnath Chatterjee.
His mortal remains will be consigned to flames day after tomorrow at 10 am in Manepura, Bhind.
Expressing grief, Madhya Pradesh Chief Minister Shivraj Singh Chouhan termed Mr Katare's demise as painful.
"I pray to the God to give strength to the bereaved to cope up with the irreparable loss," he tweeted.