For improvement of wear resistance property of atmospheric thermal plasma sprayed molybdenum (Mo) coating, diamond deposition on the atmospheric plasma sprayed molybdenum coating by the combustion flame chemical vapor deposition (CFCVD) has been operated. In this study, to diminish the thermal damage of the substrate during operation, a thermal insulator was equipped between substrate and water-cooled substrate holder. Consequently, diamond particles could be created on the Mo coating without fracture and peeling off. From these results, it was found that this process had a high potential in order to improve wear resistance of thermal sprayed coating.