The low energy densities of supercapacitors (SCs) are generally limited by the used anodes. To develop SCs with high energy densities, Fe3+ modified V2O5@GQDs (m-V2O5@GQDs) and ZIF-67-derived nanoporous carbon loaded with Mn3O4 (C/N-Mn3O4) were synthesized. After their detailed characterization using electron microscopy, X-ray methods and electrochemical techniques, they were further utilized as the anode and the cathode, respectively, to construct asymmetric supercapacitors (ASCs). The as-synthesized m-V2O5@GQDs improve the poor conductivity of V2O5, contributing greatly to a specific capacitance of 761 F g-1 at a current density of 2 A g-1. With application of a cell voltage of 2 V, an energy density of up to 99.4 W h kg-1 is achieved at a power density of 1000 W kg-1. Such ASCs also exhibit outstanding cycling performance (95% of initial capacitance even after 10 000 charging/discharging cycles). This study thus provides a new way to design and construct ASCs with high energy densities.