Hollow V2O5 microspheres (HVOM) were fabricated using NH4VO3, ethylene glycol and carbon spheres as the starting materials by a template solvothermal approach and subsequent calcination. The morphology and composition were characterized by field emission scanning electron microscopy (FE-SEM), X-ray powder diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR) and Brunauer-Emmet-Teller (BET). The results showed that the obtained HVOM were constructed from nanoparticles with rough surface. The electrochemical properties of HVOM as a supercapacitor electrode were investigated by cyclic voltammetry (CV) and galvanostatic charge-discharge (GCD). HVOM displayed excellent pseudocapacitance property and their specific capacitances were 488 F·g–1, 455 F·g–1, 434 F·g–1 and 396 F·g–1 at the current density of 0.5 A·g–1, 1 A·g–1, 2 A·g–1 and 5 A·g–1, respectively. They also exhibited an excellent energy density of 8.784 × 105 J·kg–1 at a power density of 900 W·kg–1 . The good electrochemical properties of the as-synthesized HVOM make them a promising candidate as a cathode material for supercapacitors.