Zinc electrode with polyvinyl alcohol(PVA)/poly(diallyldimethylammonium chloride) (PDDA) film coated ZnO was prepared by a chemical cross-linking method. The PVA/PDDA polymer film has an interpenetrating network structure where PVA works as polymer matrix and PDDA as anion charge carriers. Fourier transform infrared spectra (FT-IR), scanning electron microscopy (SEM) and transmission electron microscopy (TEM) studies reveal that a polymer film with well-connected three dimensional network structure is formed around ZnO nanoparticles. Linear sweep voltammetry, cyclic voltammetry (CV) and charge/discharge cycling tests were carried out on the ZnO/PVA/PDDA composite electrode, which exhibits higher electrochemical activity and dramatically superior cycle stability than the bare ZnO electrode without polymer films. The ZnO/PVA/PDDA electrode showed remarkably lower solubility during cycling.