Subrata Mukherjee, Rajiv Banerjee, Shashi Panja and Lakshmi Ratan Shukla were among the prominent Trinamool Congress MLAs to cast their votes.
CPI(M) legislator Sujan Chakraborty and Congress MLA Manoj Mukherjee also exercised their voting rights for the presidential elections which began at 10 am in the 295-member state Assembly.
The TMC, CPI(M) and Congress have already expressed support to opposition nominee, Meira Kumar.
Three MLAs from the BJP and other three from its political ally Gorkha Janmukti Morcha (GJM) -- Saritha Rai, Dr Rohit Sharma and Amar Singh Rai-- also exercised their franchise.
Legislators were not allowed to carry their personal pens inside the voting chamber and were provided with a specially-designed marker to mark their ballots as per the Election Commission's instructions.
In the presidential poll, NDA nominee Ram Nath Kovind is pitted against Congress-led opposition nominee Meira Kumar.
The counting will be undertaken on July 20.