The invention relates to a composite photocatalyst membrane material with a hierarchical pore structure and a preparation method thereof. A basal body of the composite photocatalyst membrane material is a transition a metal-doped hierarchical porous TiO2 and ZnO compound semiconductor membrane material membrane. The preparation method comprises the following steps: firstly preparing a TiO2 and ZnO compound photocatalyst precursor containing pore-forming agents P123, F127, PMMA (Polymethyl Methacrylate), PEG (Polyethylene Glycol), CTAB (Cetylt Trimethyl Ammonium Bromide) and transition metal Fe, Ni. Co, Mo, Cu, Pt, Au, Pd and Ag; then assembling the transition metal-modified ZnO/TiO2 hierarchical porous composite photocatalyst membrane material on FTO (Fluorinedoped Tin Oxide), ITO (Indium Tin Oxide) and Ni sheets and other carriers through a spray pyrolysis method, a dip-coating method, a spin-coating method, a silk-screen printing method, a doctor blade method and other coating methods; and finally, directly carrying out in-situ growth on a carbon nano tube on the composite photocatalyst membrane material through a chemical vapor deposition method. The hierarchical porous composite photocatalyst membrane material has the advantages of high photocatalytic activity, stable membrane binding, simple preparation process and easiness in industrialization realization.