Along with the assembly election, the bypoll to the Beed parliamentary seat is also being held.
Tight security has been deployed at all the 91,376 polling stations across the state, including more than 9,900 classified as "hyper-sensitive".
An electorate of around 8.35 crore is eligible to cast their votes to select their legislators from 4,119 candidates, including 276 women, in the fray.
The Beed bypoll was necessitated following the death of sitting MP, union minister Gopinath Munde, in June.
The polling started at 7 a.m. and will end at 6 p.m.