To accommodate large volume change of Cu2O for improving its supercapacitor performances, Cu2O@Ni-Al LDH core-shell structure was designed and prepared through nickel-aluminum double hydroxide grown on cubic Cu2O via a simple solvent process. The Cu2O core was wrapped by Ni-Al LDH shell, which provides a high specific area for electrochemical reaction. The results show that the specific capacitance and cycle stability of Cu2O@Ni-Al LDH are superior to those of Cu2O cubic particles. The specific capacitance of Cu2O@Ni-Al LDH hybrid electrode was up to 389 F g−1 at 1 A g−1. Furthermore, a reversible capacitance of 457 F g−1 was obtained after 12,000 cycles at a much higher current density of 10 A g−1. The enhanced performances were ascribed to the unique core-shell structure and the synergistic effects of Cu2O and Ni-Al LDH, which alleviated volume expansion and provided abundant electrochemical active sites.