ZnSe nanometer film has been synthesized on a multi-carbon nanotubes/polyvinyl alcohol (CNTs/PVA) membrane substrate by electrochemical atomic layer deposition (EC-ALD). In this work, the focal points are to optimize the ratio of CNTs/PVA conductive thin films, investigate surface morphologies of ZnxSe1-x (x = 0.3, 0.5, 0.67) and study their photoelectrical properties. The properties of CNTs/PVA composite film can be illustrated by cyclic voltammogram (CV) and Fourier transform infrared spectroscopy (FT-IR). ZnSe semiconductor film can be formed by amperometric method (I-t) according to the sequence (Se/Zn/Se/Zn ... ); the optimal deposition potential of Zn and Se can be obtained from CV. It can be observed that the morphology changed with the different proportion of Zn/Se by scanning electron microscope (SEM). When the ratio of Zn/Se is close to one, the surface morphology is the most regular and uniformity. UV-vis spectrophotometer measurements provided a band gap of 2.7 eV, which was confirmed by the absorption spectra. Open-circuit potential (OCP) indicates that ZnxSe1-x (x = 0.3, 0.5, 0.67) films have good p-type properties, three kinds of photoelectrical phenomena were observed, but the photoelectrical property of ZnSe is the best and most disciplinary in all films. This result indicates that the ZnSe film deposited on CNTs/PVA has far-reaching significance and potential application as a new solar energy cells material. (C) 2013 Elsevier Ltd. All rights reserved.