Six-time legislator Dilip Sopal on Tuesday resigned as Nationalist Congress Party MLA and is set to join the Shiv Sena on Wednesday.
Assembly Speaker Haribhau Bagde accepted Mr Sopal's resignation, a Vidhan Bhawan official said.
On Monday, Mr Sopal, NCP MLA from Barshi in Solapur district, had formally announced his decision to quit the Sharad Pawar-led party.
Mr Sopal is expected to join the Shiv Sena in the presence of the party's chief Uddhav Thackeray at a function in Mumbai on Wednesday.
Among those who left the NCP recently are former minister Madhukar Pichad, his son and party legislator Vaibhav Pichad from Ahmednagar district, legislators Shivendraraje Bhosale from Satara district, Sandeep Naik from Navi Mumbai and the party's former state women's wing chief Chitra Wagh.
All have since joined the BJP. Former state minister Jaidatta Kshirsagar, NCP's Mumbai unit chief Sachin Ahir, legislator Pandurang Barora from Thane district and party leader Rashmi Bagul from Solapur district recently joined the Shiv Sena.