The Rafales are accompanied by two A330 Phenix MRTT refuelling planes from the French Air Force.
In photos posted by the Indian Air Force on Twitter, India's first batch of Rafale fighter jets are seen re-fuelling mid-air from a French Air Force tanker before their scheduled stopover at the Al-Dhafra air base in the United Arab Emirates.
The jets built by Dassault Aviation - and piloted by officers from the Indian Air Force - took off from Merignac in southwest France, the company said in a statement.
By Wednesday, after a 7,000-km journey with the UAE pit-stop, they should be at the Ambala air base in India, some 200 kilometres from the Pakistani and Chinese borders.
They are accompanied by two A330 Phoenix MRTT refuelling planes from the French Air Force.
Delivery of the Rafale jets - 36 of which were ordered by India in September 2016 - officially began in October but the planes stayed in France for training of the pilots and mechanics. Delivery should be complete by 2022.
The five jets are the first of a batch purchased in a controversial Rs 59,000-crore inter-governmental deal by New Delhi which hopes to rapidly deploy the aircraft amid simmering tensions with China.
The Air Force has said that once the planes arrive in India, "efforts will focus on operationalisation of the aircraft at the earliest."
The Rafale fighter jets are capable of carrying a range of highly effective weapons, including the Meteor air-to-air missile and Scalp cruise missile.
The Rafale jets will come with various India-specific modifications, including Israeli helmet-mounted displays, radar warning receivers, low-band jammers, 10-hour flight data recording, infra-red search and tracking systems among others.
(With inputs from agencies)