As the voting process began in the state Assembly, legislators belonging to different political parties joined the polling process and cast their votes.
Patnaik and Mishra were among the first to cast their votes. The voting process started at 10 am amid tight security.
The other early voters were K V Singhdeo, legislator from Patnagarh, Basant Panda, BJP state unit president and former union minister Dilip Ray.
NDA's presidential candidate Ram Nath Kovind is being supported by the ruling BJD in Odisha.
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The UPA candidate Meira Kumar could not visit Odisha in the run up to the presidential election since her tour was cancelled.
While there are 117 BJD MLAs in the 147-member Odisha Assembly, the Congress has 16 legislators, the BJP 10, the CPI-M and the Samata Kranti Dal have one MLA each.
There are two independent MLAs in the house.