MoO3 thick film was manufactured by using a thermal spray process (Atmospheric Plasma Spray, or APS) and its microstructure, phase composition and properties of the coating layer were investigated. Initial powder feedstock was composed of an orthorhombic α-MoO3 phase, and the average powder particle size was 6.7 μm. As a result of the APS coating process, a MoO3 coating layer with a thickness of about 90 μm was obtained. Phase transformation occurred during the process, and the coating layer consisted of not only α-MoO3 but also β-MoO3, MoO2. Phase transformation could be due to the rapid cooling that occurred during the process. The properties of the coating layer were evaluated using a nano indentation test. Hardness and reduced modulus were obtained as 0.47 GPa and 1.4 GPa, respectively. Based on the above results, the possibility of manufacturing a MoO3 thick coating layer using thermal spray is presented.