Heterogenization of homogeneous catalyst by immobilizing complex on the surface of polymer supports promotes the design of the catalysts which combine the advantages of heterogeneous and homogeneous catalysts. The porous 2-vinyl-functional diphenyl-2-pyridylphosphine (2V-P,N) polymer (POL-2V-P,N) was successfully synthesized under solvothermal conditions. The POL-2V-P,N polymer was characterized by nitrogen physisorption, thermogravimetry (TG), scanning electron microscope (SEM) and transmission electron microscopy (TEM). The heterogenized homogeneous Pd/POL-2V-P,N catalyst was synthesized by immobilizing Pd(OAc)(2) on the POL-2V-P,N, which was used as not only support but also as ligands. The catalyst was investigated by means of P-31 NMR, X-ray absorption fine structure (EXAFS), X-ray photoelectron spectroscopic (XPS) and FT-IR and tested for the methoxycarbonylation of acetylene. According to the results of P-31 NMR, XPS and EXAFS, there existed coordination bonds between palladium and the exposed phosphorous and nitrogen atoms of,the porous POL-2V-P,N support. The XPS and FT-IR results showed that Pd-0 species were present on the Pd/POL-2V-P,N catalyst. The heterogenized Pd/POL-2V-P,N palladium complex catalyst with high surface area and large pore volume displayed excellent activity for the methoxycarbonylation of acetylene as compared with the corresponding homogeneous palladium diphenyl-2-pyridylphosphine complex (Pd-P,N) under the same conditions. The used Pd/POL-2V-P,N catalyst also exhibited excellent activity under the same conditions. In addition, the hot filtration tests indicated that the reaction occurred in a heterogeneous way. (C) 2015 Elsevier B.V. All rights reserved.