WO3 hollow nanosphere is reported using polymeric micelle with core–shell–corona architecture. Poly(styrene-b-[3-(methacryloylamino)propyl] trimethylammonium chloride-b-ethylene oxide) micelles (PS-PMAPTAC-PEO) with cationic shell block facilitates the self-assembly of hollow particles through electrostatic interaction with anionic WO4 2− precursors. X-ray diffraction (XRD) analysis confirmed the formation of pure WO3 with hexagonal lattice-structure. Transmission electron microscope (TEM) image of WO3 has confirmed the hollow structure with average outer diameter of 42±2; the hollow cavity diameter was found to be 21±1nm. The WO3 hollow nanospheres were investigated as anode materials for lithium ion battery. The nanostructured electrode delivers high initial discharge capacity of 1054mAhg−1 at a charge/discharge 0.2C. Interestingly, the hollow particles based electrodes maintain the structural integrity even after been subjected to high current density 2000Ag−1 and electrode stability.