Novel self-supported core-shell Cu2O@MnO2 octahedral microcrystals directly growing on the nickel foam have been synthesized through a facile solvothermal reduction deposition process followed by a hydrothermal reaction. The core-shell heterostructures were constructed through growing MnO2 nanosheets on the surface of Cu2O octahedral microcrystal. Based on the synergetic effects from both the cores and shells, such self-supported core-shell Cu2O@MnO2 octahedral microcrystals as binder-free electrode materials exhibited a high specific capacitance of 371Fg−1 at 0.5Ag−1 and excellent cycling stability with 95.8% of capacitance retention after 2000 cycles. These findings suggest their potential applications as a promising electrode material for supercapacitors.