Fe₂O₃-C-Ni heterojunction structured composite on foam Ni was successfully prepared by simple and effective hydrothermal reaction. The obtained material had good structural stability and excellent electrical conductivity. This binder-free Fe₂O₃-C-Ni electrode exhibits typical pseudocapacitance. Specific capacitance of Fe₂O₃-C-Ni in 1.0 mol L^-1 KOH reaches 844.6 F g^-1, which is higher than that of Fe₂O₃-Ni and C-Ni electrodes. For practice application, assembled Fe₂O₃-C-Ni//AC capacitor exhibits a long-term cycling performance with remains 79.5% capacitance retention within 20000 cycles at 1 A g^-1.