In this study, we prepared a novel poly(vinyliclene fluoride) (PVDF) membrane with poly(methacrylic acid)(PMAA) microspheres decorated by Pd nanoparticles in membrane pores and utilized the composite membrane for the catalytic reduction of p-nitrophenol. First, blending PMAA microspheres with PVDF powders formed a PVDF/PMAA blend membrane with a large quantity of PMAA microspheres in membrane pores. Subsequently, immobilization of the Pd nanoparticles on PMAA microspheres resulted in the as-prepared composite membrane. The membrane was characterized by ATR-FTIR, FESEM and EDX and applied for the catalytic reduction of p-nitrophenol under a cross-now model. Results indicate that the unique structure of composite membrane not only prevents the agglomeration of Pd nanoparticles, but also realizes the dream of timely separating highly purified products from reaction system without any additional process. The cross-flow model significantly enhances the accessibility of the catalytic active sites, makes the as-formed composite membrane display excellent catalytic activities for the reduction of p-nitrophenol to p-aminophenol. In a word, the novel composite membrane exhibits integrated merits of catalysis and separation, and shows a promising prospect for numerous catalytic applications. (C) 2015 Elsevier B.V. All rights reserved.