CO2 photocatalytic reduction is a carbon–neutral renewable energy technology. However, this technology is restricted by the low utilization of photocatalytic electrons. Therefore, to improve the separation efficiency of photogenerated carriers and enhance the performance of CO2 photocatalytic reduction. In this paper, g-C3N4/Pd composite with Schottky junction was synthesized by using g-C3N4, a two-dimensional material with unique interfacial effect, as the substrate material in combination with the co-catalyst Pd. The composite of Pd and g-C3N4 was tested to have a strong localized surface plasmon resonance effect (LSPR), which decreased the reaction barriers and improved the electron utilization. The combination of reduced graphene oxide (rGO) created a π–π conjugation effect at the g-C3N4 interface, which shortened the electron migration path and further improved the thermal electron transfer and utilization efficiency. The results show that the g-C3N4/ rGO/Pd (CRP) exhibits the best performance for photocatalytic reduction of CO2, with the yields of 13.57 μmol g− 1 and 2.73 μmol g− 1 for CO and CH4, respectively. Using the in situ infrared test to elucidate the intermediates and the mechanism of g-C3N4/rGO/Pd (CRP) photocatalytic CO2 reduction. This paper provides a new insight into the interface design of photocatalytic materials and the application of co-catalysts.