As a typical n-type semiconductor, MoO3 has been widely applied in the gas-detection field due to its competitive physicochemical properties and ecofriendly characteristics. Volatile organic compounds (VOCs) are harmful to the atmospheric environment and human life, so it is necessary to quickly identify the presence of VOCs in the air. This review briefly introduced the application progress of an MoO3-based sensor in VOCs detection. We mainly emphasized the optimization strategies of a high performance MoO3, which consists of morphology-controlled synthesis and electronic properties functional modification. Besides the general synthesis methods, its gas-sensing properties and mechanism were briefly discussed. In conclusion, the application status of MoO3 in gas-sensing and the challenges still to be solved were summarized.