In our previous study, it was proved that diamonds could be deposited on thermal spray coated substrate without peeling of and break down of the thermal spray coating even in case of combustion flame CVD by cooling substrate surface during deposition. In this study, to develop easy diamond/metal binary coating deposition process, diamond deposition on the as-deposit thermal sprayed Mo coating was carried out. Consequently, even in case of as-deposit Mo coating, diamonds could be deposited and rigid diamond/Mo complex coating could be deposited by additional Mo thermal spraying after diamond deposition. Besides, the complex coating had higher wear resistance in comparison with the normal Mo thermal spray coating.