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MoO3 was synthesized by thermal decomposition of ammonium molybdate. The structure and surface morphology of the as-prepared MoO3 was characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The supercapacitive behaviour of MoO3 in 1 mol L-1 KCl electrolyte was studied by cyclic voltammetry (CV), galvanostatic charge-discharge cycling (CD). The affect of thermal decomposition temperature on the capacitive behaviour of MoO3 was also discussed here. The results indicate that MoO3 show good capacitive behaviour with a specific capacitance of 148.9 F g-1 at 0.7 A g-1. Thermal decomposition temperature has an important influence on the capacitive behaviour and crystallization of MoO3.