Hierarchical porous γ-Fe 2 O 3 @SiO 2 @TiO 2 (FST) composite microspheres with sandwich-like structure were fabricated by an effective three-step approach. Specifically, the preformed monodisperse Fe 3 O 4 spheres were used as templates for directing the sequential deposition of SiO 2 layer by modified Stöber method and subsequent TiO 2 layer by vapor–thermal route. Notably, the interior black Fe 3 O 4 templates are converted into dark-brown γ-Fe 2 O 3 during the vapor–thermal assisted TiO 2 deposition. By introducing a SiO 2 layer between the γ-Fe 2 O 3 core and TiO 2 shell, while the superparamagnetic properties was remained to great extent, the photocatalytic activity towards degradation of rhodamine B (RhB) dye molecules was also significantly improved, as compared to that of the Fe 3 O 4 @TiO 2 (FT) counterparts. This enhancement in photoactivity is mainly attributed to two positive effects of the interbedded SiO 2 layer between the γ-Fe 2 O 3 core and TiO 2 shell. Firstly, a direct contact and electron injection from TiO 2 to γ-Fe 2 O 3 is blocked by this wide bandgap SiO 2 electronic barrier, which avoids charge recombination at the interface. Secondly, a SiO 2 middle layer is a good adsorbent towards dye molecules, which enhances the enrichment of pollutant dye molecules around the porous titania photoactive layer and thus the photocatalytic efficiency. Such a novel multifunctional photocatalytic integrated microspheres can effectively degrade organic pollutants and can be easily recovered by a magnet, which was reused at least five times without any appreciable reduction in photocatalytic efficiency.