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In this work, the unique starlike La-doped ZnO-SiO2 photocatalysts were constructed by an evaporation and calcination method and characterized in detail. UV-vis reflectance and DFT calculation confirm that the doping with La allows to obtain a decrease of band gap of ZnO/SiO2, which enhances visible light absorbance and oxidizing ability. The photoluminescence intensity reduces greatly, indicating more effective separation of the photogenerated carriers of La-doped ZnO-SiO2. Photocatalytic activities of La-doped ZnO-SiO2 with different doping ratios under simulated visible light irradiation were evaluated with malachite green (MG) as a model pollutant. Under optimized conditions including solution pH of 8, 15 mg/L of MG solution and 15 mg of catalyst dosage, 0.2％La-ZnO-SiO2 exhibits the best catalytic activity in photodegradations of MG in water. The removal and mineralization efficiency of MG can reach 96.1％and 70.9％in 140 min, respectively. The as-prepared catalysts present superior stability and recyclability after four times reuse. Moreover, selective quenching experiments indicate that hydroxyl radical (?OH), hole (h+) and superoxide radical (?O2-) are the main reactive species responsible for MG degradation. Possible mechanism for photocatalytic elimination of MG over La-doped ZnO/SiO2 photocatalyst is finally proposed.