We report a heterojunction composite of V2O5 nanobelt arrays/TiO2 nanoflake arrays grown directly on nickel foam. The morphology evolution and growth mechanism of TiO2 nanoflake arrays on V2O5 nanobelt arrays are investigated in detail. The heterojunction composite nano-arrays have a large specific capacitance of 587 F g(-1) at a current density of 0.5 A g(-1), a high coulombic efficiency (> 92%), an excellent cycle stability (92%) after 5000 cycles and a low charge transfer resistance of 2.6 Omega. When the heterojunction composite nano-arrays are assembled into symmetric supercapacitor, the device shows a high energy density of 100.8 W h kg(-1) at a power density of 399 W kg(-1). The high supercapacitive performance is attributed to their direct growth on conductive current collector and the synergistic effect of V2O5 and TiO2.