In the last years, supercapacitors (SCs) have been proposed as a promising alternative to cover the power density deficiency presented in batteries. Electrical double-layer SCs, pseudocapacitors, and hybrid supercapacitors (HSCs) have shown very attractive features such as high-power density, long cycle life, and tunable specific capacitance. The advances of these energy storage devices made by transition metal oxides (TMOs) and their production in pseudocapacitors and HSCs depend on chemical composition, crystalline structure,morphology, theoretical capacitance, and oxidation states. In this way, this critical review considers several metal oxides (RuO2, MnO2, V2O5, and Co3O4) and their different configurations with diverse carbon-based materials. Energy storage mechanisms and fundamental principles to understand the promising effect of metal oxides in SCs devices are thoroughly described. Special attention as regards to the energy storage mechanisms relative to the specific capacitance values is presented in the reviewed articles. This review envisages the TMOas a key component to obtain high specific capacitance SCs.