The construction of multicomponent hybrid nanomaterials with well-controlled architecture, especially bearing an ordered homogeneity and distribution of the subunits with tunable functions, is a key challenge in chemistry and material science. Herein, we reported a versatile and novel strategy to fabricate core–satellite multicomponent nanostructures with tunable interparticle distances and catalysis properties by the combination of surface-initiated reversible addition–fragmentation chain transfer (SI-RAFT) polymerization and self-assembly. The arrangement and interparticle distance of gold satellites could be precisely tuned by the SI-RAFT polymerization process and the feeding ratio of gold nanoparticles (AuNPs) and the core nanoparticle. It is worth to note that multilayered core–satellite nanostructures have been fabricated by a high-feeding ratio of AuNPs and magnetite NP (MNP)@SiO2–PNIPAm. Notably, the core–satellite MNP@SiO2–PNIPAm–Au nanoparticles exhibited excellent thermoresponsive behaviors with the change of temperature. Furthermore, the catalytic efficiency of MNP@SiO2–PNIPAm–Au nanoparticles via the reduction of 4-nitrophenol to 4-aminophenol can be well modulated by the nanoparticle size, temperature, and polymer feed ratio. This strategy for precise construction of core–satellite nanostructures would open a new pathway to construct multicomponent functional nanostructures.