This study reported the improved Raman enhancement ability of silver nanoparticles (Ag NPs) decorated on surface mesoporous silica microspheres (MSiO2@Ag) than that of Ag NPs on solid silica microspheres (SSiO2@Ag). These two kinds of hybrid structures were prepared by a facile single-step hydrothermal reaction with polyvinylpyrrolidone (PVP) serves as both a reductant and stabilizer. The as-synthesized MSiO2@Ag microspheres show more significant surface-enhanced Raman scattering (SERS) activity for 4-mercaptobenzoic acid (4MBA) than SSiO2@Ag microspheres with enhancement factors as 9.20 x 10(6) and 4.39 x 10(6), respectively. The proposed reason for the higher SERS activity is estimated to be the contribution of more Raman probe molecules at the mesoporous channels where an enhanced electromagnetic field exists. Such a field was identified by theoretical calculation result. The MSiO2@Ag microspheres were eventually demonstrated for the SERS detection of a typical chemical toxin namely methyl parathion with a detection limit as low as 1 x 10(-3) ppm, showing its promising potential in biosensor application. (C) 2016 Elsevier B.V. All rights reserved.