In recent years, a promising role of plasmonic metal nanoparticles (NPs) has been demonstrated toward an improvement of the catalytic efficiency of well‐designed hybrid electrocatalysts. In particular, the coupling of plasmonic functionality with the metal‐based core–shell architectures in plasmon‐enhanced electrocatalysis provides a sustainable route to improve the catalytic performances of the catalysts. Herein, the rationally designed AuNPs wrapped with reduced graphene oxide (rGO) spacer along with PdNPs (AuNP@rGO@Pd) as the final composite are reported. The rGO is proposed to promote the reduction of PdO, greatly enhance the conductivity, and catalytic activity of these nanohybrid structures. The plasmon‐enhanced electrocatalytic performance of optimized AuNP@rGO(1)@Pd exhibits an ≈1.9‐ and 1.1‐fold enhanced activity for the hydrogen evolution reaction and oxygen evolution reaction, respectively. The final composite also exhibits a superior stability up to 10000 s compared with the commercial Pd/C. The mechanism of the enhanced catalytic performance is monitored through in situ X‐ray absorption spectroscopy by observing the generated electron density under light irradiation. The results demonstrate that the energetic charge carriers are concentrated in the incorporated PdNPs, allowing higher catalytic performances for the overall water‐splitting reaction. The conclusions herein drawn are expected to shed light on upcoming plasmon‐induced electrocatalytic studies with analogous hybrid nanoarchitectures.
