We attempted the photo-chemical recovery of noble metals from solutions using inorganic-organic hybrid photocatalysts based on polyoxometallates (POMs) such as PMo12O403-, SiW12O404-, and γ-SiW10O368- coupled with a cationic surfactant, dimethyldioctadecylammonium (DODA). We also used γ-SiW10O36-O(SiC18H37)2 as a photocatalyst. The four different photocatalysts dissolved in chloroform successfully photoreduced gold ions dissolved in water in a two-phase (chloroform/water) system under UV irradiation (λ< 475 nm). The γ-SiW10O36/DODA photocatalyst exhibited the best activity and was able to recover gold from solution. It was suggested that one-electron reduced γ-SiW10O369-, which was formed by UV irradiation, reduced gold ions to produce large two-dimensional particles. The formation of sheet-like particles indicates that the reduction of gold ions occurred at the interface between chloroform and water.