Our study reports a novel iron oxide/noble metal/semiconductor ternary multilayer hybrid structure that was synthesized through template synthesis and layer-by-layer deposition. Three different morphologies of α-Fe2O3/Ag/SiO2/SnO2 hybrid architectures were obtained with different thicknesses of the SiO2 interlayer which was introduced for tailoring and controlling the coupling of noble metal Ag nanoparticles (NPs) with the SnO2 semiconductor. The resulting samples were characterized in terms of morphology, composition, and optical property by various analytical techniques. The as-obtained α-Fe2O3/Ag/SiO2/SnO2 nanocomposites exhibit enhanced visible light or UV photocatalytic abilities, remarkably superior to commercial pure SnO2 products, bare α-Fe2O3 seeds, and α-Fe2O3/SnO2 nanocomposites. Moreover, the sample of α-Fe2O3/Ag/SiO2/SnO2 also exhibits good chemical stability and recyclability because it has higher photocatalytic activity even after eight cycles. The origin of enhanced photocatalytic activity on the multilayer core-shell α-Fe2O3/Ag/SiO2/SnO2 nanocomposites was primarily ascribed to the coupling between noble metal Ag and the two semiconductors Fe2O3 and SnO2, which are proven to be applied in recyclable photocatalysis.