A controllable structure of organic–inorganic hybrid particle clusters (HPCs) with directionally distributed bimetal was produced through the self-assembly of organic poly(styrene-co-glycidyl methacrylate-co-vinylbenzoic acid) (PSGV) and γ-aminopropyltriethoxysilane-modified inorganic SiO₂&Au nanoparticles (NPs), during which the strong interaction between the carboxyl groups of the organic particles and the amino groups of the inorganic particles played a key role in self-assembly. Controlling the mean size and feeding route of the above two particles allowed strawberry-shaped PSGV&Ag@SiO₂&Au and SiO₂&Au@PSGV&Ag HPCs with exchangeable core and corona to be obtained. The scanning electron microscopy and transmission electron microscopy study results demonstrated that surface of the PSGV domains was embellished with Ag NPs from the chemical bonding between silver ions and amino groups, which were obtained by later modification of PSGV@SiO₂&Au, while the Au NPs were only seen on the surface of the SiO₂&Au domains. The resultant PSGV&Ag@SiO₂&Au particles showed an excellent performance in the catalytic degradation of Rhodamine B, where an above 99% degradation efficiency can be gained within 3 min. The improvement of catalytic activity was ascribed to the unique morphological structure of the HPCs and synergistic effect of the directionally distributed Au and Ag NPs.