We report here successful synthesis of superoleophilic, nanoporous polymeric ionic liquids supported palladium acetate (PDVB-[C(3)vim][SO3CF3]-Pd-xs, where x stands for the weight percentage of palladium acetate), which act as efficient heterogeneous catalysts in Suzuki-Miyaura cross-coupling reaction. PDVB-[C(3)vim][SO3CF3] support was synthesized from solvothermal copolymerization of divinylbenzene with vinylimidazole without using any templates, followed by functionalized with ionic liquid groups. The resultant PDVB-[C(3)vim][ SO3CF3]-Pd-xs possess large BET surface areas, good stability, homogeneous dispersion of Pd active species, and superwettability for various aromatic reactants, which result in their much improved reactants enrichment property. The above characters make PDVB-[C(3)vim][SO3CF3]-Pd-xs showed much improved catalytic activity and good recyclability in Suzuki-Miyaura reaction in comparison with those of palladium acetate supported onto activated carbon and ordered mesoporous silica of SBA-15. The superior activity found in PDVB-[C(3)vim][SO3CF3]-Pd-xs is attributed to synergistic effects between large surface areas and unique enrichment property for various aromatic reactants, which by themselves are capable of enhancing exposition degree of Pd active sites to reactants. (C) 2014 Elsevier Inc. All rights reserved.