Plasmonic photocatalysis caused by surface plasmon resonance (SPR) has emerged out as an impressive way for efficient light absorption and solar light conversion. A series of catalysts consisting of plasmonic Ag nanoparticles (NPs) deposited on CeO2 coated mesoporous silica, SBA-15, prepared by MW-assisted alcohol reduction method were tested for the chemoselective hydrogenation of p-nitrostyrene. A remarkable increase in the reaction rate occurred when the catalyst support contained specific composition (2 wt %) of CeO2 on silica. The structure and properties of the prepared catalysts were studied by using a range of physicochemical characterization tools; UV-vis, transmission electron microscopy (TEM), X-ray absorption fine structure (XAFS), X-ray photoelectron spectroscopy (XPS) and N-2-physisorption measurement studies. The challenging reduction of p-nitrostyrene containing an easily reducible group was examined in an ethanol suspension under mild reaction conditions using ammonia borane (AB) as an in-situ source of hydrogen. The highest conversion (100%) and 90% product yield in the hydrogenation of p-nitrostyrene to p-aminostyrene was achieved on the catalyst with 1.0 wt % loading of Ag NPs and 2 wt % of CeO2 supported on silica.