Two salt-free Zn(2+)-ligand-coordinated vesicle phases were prepared from the mixtures of alkyldimethylamine oxide (C(n)DMAO, n = 14 and 16, i.e., C(14)DMAO and C(16)DMAO) and zinc laurate [(CH(3)(CH(2))(10)COO)(2)Zn] in aqueous solution. The two salt-free Zn(2+)-ligand-coordinated vesicle phases were subsequently used as the templating media for fabricating zinc nanoparticles on an indium-doped tin oxide (ITO) electrode via electrodeposition. Influence of temperature, direct current density, and composition of the surfactant mixtures on the average diameter and size distribution of Zn nanoparticles was investigated in more detail. The structure of Zn@ITO was determined by scanning electron microscope and energy-dispersive X-ray spectroscopy analysis. Monodispersed Zn nanoparticles on ITO electrode (ZnNPs@ITO) with different average diameters were obtained, and the distribution can be controlled. Finally, ZnO nanostructures on the ITO substrate were prepared from the as-synthesized Zn@ITO nanoparticles through electrochemical surface oxidation. The preparation of nanostructured Zn and ZnO particles by our established method may pave the way for a new templating route from metal-ligand-coordinated vesicles.