Integration of localized surface plasmon resonance (LSPR) metallic nanocrystals into photocatalysis is an intriguing approach for light‐driven organic transformations. However, uncertain direction of hot carriers is a grand challenge, which fails to take full advantage of the LSPR excitation. In this work, core–shell gold@ceria nanosphere–supported segregated palladium species (Au@CeO2–Pd) have developed to steer the light absorption capability and charge carrier migration. Under simulated solar light irradiation, the core–shell–satellite Au@CeO2–Pd exhibited efficient light harvesting and colossal activity in the Suzuki coupling reaction. The plasmon‐induced hot electrons overpassed the Schottky barrier at the Au@CeO2 interfaces and migrated from Au core to CeO2 shell accordingly. Subsequently, the photogenerated electrons and hot electrons migrated from Au@CeO2 core–shells to Pd, which acted as an electron acceptor. Detailed photocatalytic mechanism studies revealed that both photoexcited electrons and holes were the main active species involved in the photocatalytic Suzuki coupling reaction process. In particular, the diphenyl yield over Au@CeO2–Pd catalyst was ~1.7 times higher than that of core–shell–satellite Au@SiO2–Pd, where a 19‐nm‐thick SiO2 shell was introduced to prevent the migration of hot electrons. This distinctly certified that the hot electrons transfer in the core–shell–satellite Au@CeO2–Pd under illumination played an important role to drive Suzuki reaction. Overall, this design of core–shell–satellite Au@CeO2–Pd plasmonic photocatalyst has the potential in the field of photo‐driven organic transformations.