Recycling of spent domestic batteries has gained a great environmental significance. In the present research, we propose a new and simple technique for the recovery of high-purity zinc oxide nanoparticles from the electrode waste of spent alkaline Zn–MnO2 batteries. The electrode material was collected by the manual dismantling and mixed with 5M HCl for reaction with a phosphine oxide reagent Cyanex 923® at 250°C for 30min. The desired ZnO nanoparticles were restored from the Zn-Cyanex 923 complex through an ethanolic precipitation step. The recovered particle product with about 5nm diameter exhibited fluorescent properties (emission peak at 400nm) when excited by UV radiation (excitation energy of 300nm). Thus, the proposed technique offered a simple and efficient route for recovering high purity ZnO nanoparticles from spent alkaline batteries.