As the Assembly complex is undergoing renovation, the voting is taking place at Swarnim Sankul-2 complex inside the secretariat.
Anandiben Patel, who is the MLA from Ghatlodia in Ahmedabad, cast her vote.
NDA candidate Ram Nath Kovind was in Gandhinagar on Saturday to seek support of BJP MLAs and MPs. UPA candidate Meira Kumar visited Gujarat last month to launch her campaign from the iconic Sabarmati Ashram.
Congress chief whip Balwantsinh Rajput said MLAs and MPs can also cast votes in Delhi.
Meanwhile, rebel BJP MLA Nalin Kotadia said he will vote against the NDA candidate to protest alleged "atrocities" against members of the Patel community during the 2015 quota agitation.
Mr Kotadia was suspended from the party recently. The ruling BJP has 122 MLAs in Gujarat, while the Congress has 57, the NCP two and the JD(U) one in the 182-member Assembly.
In the Lok Sabha, all 26 MPs from the state belong to the BJP.
BJP president Amit Shah, the MLA from Naranpura constituency in Ahmedabad, will cast his vote in Delhi, party sources said.