The deceased was identified as Manoranjan Behera. His wife Renubala sustained injuries in the incident, when the couple was on their way to Puri.
Police said the two bike-borne youths intercepted the couple and tried to snatch a gold chain from Renubala.
As the husband opposed their bid, they opened two rounds of fire, one of which hit Manoranjan on the chest. He died on the spot, while wife Renubala was shifted to Puri District Headquarters Hospital for treatment.
"The police have recovered an empty cartridge from a place about 100 meters from the attack site. We also suspect it could be a pre-planned murder," said Mrutunjay Swain, Inspector in-charge of Satyabadi Police Station.
Puri SP Sarthak Sarangi said the police have intensified patrolling and taking steps to nab the two miscreants who fled from the place after killing the man.
"The youths followed us from a distance and opened fire as my husband resisted the snatching of the gold chain from me. One bullet missed me, another hit my husband," an injured Renubala said.