The increasing worldwide interest in MnO2 for supercapacitor applications is based on anticipation that MnO2-based high-voltage aqueous supercapacitors will ultimately serve as a safe and low-cost alternative to state-of-the-art commercial organic-based electrochemical double-layer capacitors or RuO2-based acid systems. In this paper, the physicochemical features, synthesis methods, and charge storage mechanism of MnO2 as well as the current status of MnO2-based supercapacitors are summarized and discussed in detail. The future opportunities and challenges related to MnO2-based supercapacitors have also been proposed.