We report here an efficient mesoporous polymeric solid acid catalyst (p-PDVB-SO3H) with superhydrophobic-oleophilic properties synthesized from copolymerization of divinylbenzene (DVB) with sodium p-styrene sulfonate under solvothermal conditions. N-2 isotherm showed that p-PDVB-SO3H has large BET surface area and uniform mesopore. Contact angle tests showed that p-PDVB-SO3H exhibits superhydrophobic-oleophilic property for triolein and methanol, which results in its good miscibility and high exposition degree of active sites for various organic reactants. Catalytic tests showed that p-PDVB-SO3H has much better catalytic activities and recyclability toward transesterification to biodiesel than those of H-form mesoporous ZMS-5 zeolite, carbon solid acid and commercially acidic resin of Amberlyst 15, which will be very important for its wide applications for biodiesel production in industry.