Display omitted •Ag and Pd are anchored on SrBi2Ta2O9 to construct CO and CH4 evolution sites.•Ag and Pd attract and accumulate the electrons originating from SrBi2Ta2O9.•The intermediate species CO* desorb and form CO directly on the surface of Ag.•The CO* is further hydrogenated to form CH4 on the surface of Pd. Photocatalytic CO2 reduction in presence of H2O provides an ideal way to alleviate the greenhouse effect and obtain valuable chemicals. Constructing active sites on the surface of photocatalysts significantly affects the activity and selectivity of photocatalytic CO2 reduction, which involves a multi-electron reduction process. Herein, we anchor Ag and Pd particles on the surface of layered perovskite SrBi2Ta2O9 to build CO and CH4 evolution sites, respectively, via a photodeposition method. Ag and Pd not only attract and accumulate the photoinduced electrons originating from SrBi2Ta2O9 due to the formed Schottky junction between them, but also activate CO2 molecules, thereby resulting in higher CO2 reduction activity. On the surface of Ag, intermediate species CO* desorb and form CO directly, whereas, on the surface of Pd, intermediate species CO* is further hydrogenated to form CH4, thus resulting in different selectivity. This work offers a new avenue for developing photocatalysts with high activity and selectivity for CO2 reduction.