For the first time, nonstoichiometric WO2.72 was used as a counter electrode (CE) in dye-sensitized solar cells (DSSCs). Oxygen-vacancy-rich WO2.72 nanorod bundles with notable catalytic activity for triiodide and thiolate reduction were prepared in this study. The photovoltaic parameters of dye-sensitized solar cells (DSSCs) with WO2.72 nanorod bundles as CEs are superior compared with those of the WO3-based cells, and nearly the same as those of the precious metal Pt-based cells. In a non-corrosive organic redox couple, the performance of WO2.72 CEs is better than that of Pt and WO3 CEs in DSSCs.