MoO3and MoO2materials have been successfully synthesized by thermal decomposition of ammonium paramolybdate in air and a sealed quartz tube, respectively. The microstructure of as‐synthesized MoO3is composed of irregular lamellar plates with a plate thickness around 100 nm and MoO2has the larger grain size with lamellar plates connected with each other. A maximum specific capacitance of 318 F/g at 0.5 A/g is obtained for MoO2prepared in a closed environment. On the other hand, the sample MoO3exhibits excellent rate capacity with specific capacitances of 218, 209, 196, 188, 176, and 160 F/g at current densities of 0.5, 1, 2, 3, 4, and 5 A/g, respectively. These results pave the way to consider MoO3and MoO2as prospective materials for energy‐storage applications.