Patole, elected from Bhandara-Gondiya, said he submitted his resignation to Lok Sabha Speaker Sumitra Mahajan's office and also to the Bharatiya Janata Party leadership. He said he was "deeply anguished and felt let down by the party".
His brief resignation letter addressed to Mahajan read: "Respected Madam, I hereby tender my resignation of my seat in the House with effect from today i.e. 08/12/17."
The development is seen as a blow to the BJP, coming a day ahead of the first round of the Gujarat Assembly polls on Saturday.
"The objectives with which I had joined the (BJP) party have been belied, but now (post-quitting) I am free of the turmoil in my mind," Patole told the media shortly after submitting his resignation letter to the Lok Sabha Secretariat.
He said he had not made up his mind on which party to join but would consider throwing his lot with "some like-minded" political outfit.
Patole created a sensation in September when he told a public function that Modi doesn't like to be questioned and criticized.
He also alleged that all central ministers "were always in a state of fear" and that he was "on the hit list but I am not afraid of anyone".