Raspberry-like hollow-spheres-on-sphere (HSOS) particles with reactive surfaces, uniform sizes and monodisperse properties were rational designed and fabricated to immobilize gold nanoparticles for the catalytic reduction of 4-nitrophenol. HSOS polysilsesquioxane (PSQ) particles were constructed by an organic alkali catalyzed sol-gel process from trialkoxysilane precursors with stabilized polystyrene (PS) nanoparticles as both a sacrifice template and a Pickering emulsifier. The PSQ particles were fabricated in an ice bath with methyltrimethoxysilane and mercaptopropyltrimethoxysiane as a co-precursor, tetramethylammonium hydroxide (TMAH) as a catalyst, polyvinylpyrrolidone (PVP) and sodium lignosulfonat as co-stabilizers and PS latex as a hard template. The formation mechanism of the hierarchical particles was investigated in detail by the time study through imaging the particles at regular time intervals during the reaction process. Various effect factors on the morphology were studied systematically which showed that the precursor composition, the content of PS, TMAH and PVP are the most important factors. The hierarchical structure combined with the mercaptopropyl groups on both the surface and the skeleton to make it possible to adsorb guest molecules. Au nanoparticles were immobilized on the particles for the catalytic reduction of 4-nitrophenol to 4-aminophenol. The unique PSQ colloids with hollow-spheres-on-sphere extended the family of the hierarchical structures and has shown the potential applications in separations, drug delivery and heterogeneous catalysts.