World Championship silver medallist Rai shot 235.1 to comfortably finish top of the podium.
Mitharwal, who had established a new qualification record with 584, eventually finished with the bronze medal after aggregating 214.3 in the eight-man finals at the Belmont Shooting Centre.
Australia's Kerry Bell managed to secure the silver medal with 233.5.
In the finals, Jitu led with 100.4 at the end of stage 1, while Mitharwal was third with 98.1.
In stage 2 elimination, Rai started with 10.3 and 10.3 to lead the pecking order, even as his compatriot moved up and displaced Bell at second place with two 10.1s. Championship.
Rai continued to surge ahead with a 10.2 but an 8.4 disturbed his momentum somewhat, as the next shot fetched him 9.2.
Meanwhile, Mitharwal closed the gap as Rai had just 8.8 in the 18th shot to Mitharwal's 10.0.
However, Mitharwal slipped after that even as Rai managed another 10.0 and maintained the lead throughout to emerge triumphant.