A new strategy involving the introduction of the common cationic surfactant cetyltrimethyl ammonium bromide (CTAB) for the cathodic electrodeposition of ZnO electrodes from Zn(NO3) solutions by cyclic voltammetry has been developed. Frizzily lamellar and porous ZnO films were obtained. The deposited films were characterized by X-ray diffraction (XRD) in the range of low-angle and wide-angle, X-ray photoelectron Spectroscopy (XPS), scanning electron microscopy (SEM), and UV-Vis transmittance spectroscopy. The role of the CTAB was also discussed. Under the optimal contents of CTAB, the XRD pattern shows that the as-synthesized ZnO is lamellar nanostructure and SEM image demonstrates that porous and frizzyly lamellar ZnO crystals are formed; XPS spectra of as-deposited film shows that the electrodeposition mainly consists of Zn and O and the Optical transmittance spectra of ZnO film indicates that optical transmittance is low and gradually decreases with the wavelength lessening in the visible light region. Mechanisms are proposed for the electrochemical deposition and the beneficial role of CTAB.