Catalytically active Au@hollow-SiO2 particles embedded in porous silica support (Au@hollow-SiO2@PSS) were prepared by using spherical micelles from poly(styrene)-block-poly(4-vinyl pyridine) block copolymer as a sacrificial template. Drastic increase of the shell porosity was observed after pyrolytic removal of polymeric template because the stretched poly(4-vinyl pyridine) chains interpenetrating with silica shell acted as an effective porogen. The embedding of Au@hollow-SiO2 particles in porous silica support prevented their fusion during pyrolysis. The catalytic activity of Au@hollow-SiO2@PSS was investigated using a model reaction of catalytic reduction of 4-nitrophenol and reductive degradation of Congo redazo-dye. Significantly, to the best of our knowledge, Au@hollow-SiO2@PSS catalyst shows the highest activity among analogous systems reported till now in literature. Such high activity was attributed to the presence of multiple pores within silica shell of Au@hollow-SiO2 particles and easy accessibility of reagents to the catalytically active sites of the ligand-free gold surface through the porous silica support. (C) 2016 Elsevier Inc. All rights reserved.