Urchin-like tungsten oxide (WO3) microspheres self-assembled with nanobelts are deposited on the surface of the hydrophilic carbon cloth (CC) current collector via hydrothermal reaction. The WO3 nanobelts in the urchin-like microspheres are in the hexagonal crystalline phase, and their widths are around 30–50 nm. The resulted hierarchical WO3 / CC electrode exhibits a capacitance of 3400 mF / cm2 in H2SO4 electrolyte in the voltage window of −0.5 ~ 0.2 V, which makes it an excellent negative electrode for asymmetric supercapacitors. To improve the capacitive performance of the positive electrode and make it comparable with that of the WO3 / CC electrode, both the electrode material and the electrolyte have been carefully designed and prepared. Therefore, the hydrophilic CC is further coated with carbon nanotubes (CNTs) to create a hierarchical CNT / CC electrode via a convenient flame synthesis method, and a redox-active electrolyte containing an Fe2+ / Fe 3+ couple is introduced into the half-cell system as well. As a result, the high performance of the asymmetric supercapacitor assembled with both the asymmetric electrodes and electrolytes has been realized. It exhibits remarkable energy density as large as 403 μW h / cm2 at 15 mW / cm2 and excellent cyclic stability after 10,000 cycles.