Abstract: The development and utilization of hydrogen could be an effective way to solve the problem of energy crisis and environmental pollution. In order to improve the efficiency of hydrogen production of the industrial alkaline water electrolysis, it is worth considering the combination of water electrolysis with photo-catalytic decomposition of water for producing hydrogen. Water electrolysis assisted by photo-catalysis for hydrogen production has been studied, while the key technology is the anode modified by photo-catalyst. It's well known that TiO₂ has the defects of low utilization of visible light and low quantum yield, thus it is necessary to improve photo-catalytic properties of TiO₂ by metal ion doping, semiconductor recombination, noble metal deposition and structured regular nanostructures. Meanwhile, carbon nanotubes (CNTs) have unique mechanical and electrical properties that can enhance the structural stability and electron transport rate of the material. And in the photo-catalytic process, CNTs have an important role in increasing the separation efficiency of photo-generated carriers. Using polystyrene microsphere as template, highly ordered TiO₂-ZnO porous composite film doped with iron and nickel were prepared on the FTO and Ni anode by sol-gel method. Using the doped iron and nickel as catalyst, after growing CNTs by in-situ chemical vapor deposition (CVD) on Fe-Ni-TiO₂/ZnO, CNT/Fe-Ni-TiO₂/FTO (Ni) of porous composite film with three dimensional porous structure was fabricated. The analysis of scanning electron microscopy (SEM) indicated that the composite film present highly ordered porous construction when V(TiO₂):V(ZnO) in the precursor of TiO₂-ZnO was 3:2. The structure and properties of composite film were characterized by X-ray diffraction (XRD), UV-vis absorption, electro-chemical-impedance spectroscopy (EIS), and water electrolysis assisted by photo-catalysis(WEAP). Compared with nickel anode, the hydrogen production activity of CNTs/TiO₂-ZnO porous membrane modified nickel electrode was increased by 307.4%. The experimental results showed that the separation effect of electron-hole pair and photo-catalytic activity of the composite film would be promoted by the ordered porous structures, TiO₂-ZnO hetero-junctions and the three dimensional porous structure.