ZnO/NiO/ZnAl₂O₄ mixed metal oxides were synthesized through a facile and environment-benign route in which solutions of appropriate amounts of metal salts were mixed with solutions of sodium hydroxide and sodium carbonate to obtain a series of hydrotalcite-like precursors. The precursors in the form of ZnNiAl layered double hydroxides (LDHs) were subject to calcination at suitable temperatures for the generation of composite oxides. The as-obtained samples were characterized by XRD, SEM, TEM, EDS, BET and UV-Vis DRS techniques. The results indicate that there is the generation of well-crystalline ternary ZnO/NiO/ZnAl₂O₄ photocatalysts high in surface area. The photocatalytic activity of the as-obtained materials was evaluated in the photocatalytic reduction of CO₂ under simulated sunlight irradiation. The effects of calcination temperature,amount of sacrificial agent and reaction time on the photocatalytic activity of the samples were investigated. The results indicated that ZnNiAl-LDH precursor calcined at 500 °C show the highest photocatalytic activity, the maximum yield of 2680 umolgcat^-1 methanol within 6 h was obtained with 0.04 mol of NaOH and Na₂SO₃, respectively. The mechanism of CO₂ photocatalytic reduction over ZnO/NiO/ZnAl₂O₄was discussed.