An 18-seater airplane was flagged off by city Airport Director Suresh Chandra Hota. It is the maiden air passenger service between the two cities.
On the first day, the flight started its journey with nine passengers on board. The return flight is expected to land after 1 p.m.
As per the schedule, the first flight will depart Bhubaneswar at 6.10 a.m, and arrive at Raipur at around 7.40 a.m.
The return flight from Raipur will begin at 12.15 p.m. and reach Bhubaneswar at 1.40 p.m.
The flight will be available six days a week except for Sunday, said an official.
"There was no air connectivity between Bhubaneswar and Raipur. With this, we hope the passenger service will increase between the two cities," said Mr Hota.
The aircraft will have two pilots and one crew member.
The carrier won the rights to fly on 50 regional routes and had received its scheduled commuter operator permit from the Director General of Civil Aviation (DGCA) in February.
"However, the flight service of Air Odisha between Bhubaneswar and Raipur does not come under the UDAN regional connectivity scheme", said Mr Hota.
Sources said the carrier would also connect Jharsuguda and Rourkela in the coming days.