The polling was held at the Legislature complex here.
The ruling front, which has 73 MLAs, and 52 MLs of the LDF belonging to CPI(M), JD(S) and NCP are supporting UPA nominee Pranab Mukherjee.
Thirteen CPI and two RSP MLAs abstained from voting as per the decision of their national leadership.
CPI-M MLA Thomas Isaac cast his vote in New Delhi.
Chief Minister Oommen Chandy, Opposition Leader V S Achuthanandan and CPI(M) polit buro members Kodiyeri Balakrishnan and M A Baby were among the early voters.