A hierarchical furball-like WO₃ electrode material, based on stainless-steel mesh, was successfully synthesized via a simple in situ hydrothermal method. The electrode materials obtained are made from a self-assembled nanorod core and a connected/quasi-connected nano-thorn network shell, and could help utilize all the surface or near-surface regions for faradaic reaction. Furthermore, the furball-like WO₃ special microstructure provides a more effective charge storage area, exhibiting a high specific capacitance of 8.35 F cm⁻² and excellent cycling stability (93.4% of its initial value after 10 000 cycles). These performances indicate this furball-like WO₃ material would be a promising candidate for high performance supercapacitors.