Polydivinylbenzene (PDVB) beads with high specific surface area and excellent pore connectivity were prepared by traditional suspension polymerization, through poly(ethylene-b- propylene) (PEP) and toluene (TOL) as a novel co-porogen. PEP concentration in co-porogen was changed to investigate PEP amount on the pore structure of PDVB beads. The surface morphology of PDVB beads was observed by SEM, and the pore structure and the pore size distribution curves were characterized by N2 sorption and Hg intrusion technique. The results indicated that co-porogen of 2.0% PEP in TOL induce double phase separation. PEP induce an early phase separation due to PEP being incompatible with PDVB network, and TOL induce a late phase separation as TOL is a thermodynamically compatible solvent for PDVB network. Double phase separation have significant effect on the pore connectivity, the specific surface area, the pore volume, and the average pore diameter of PDVB beads. Overall, the present manuscript provide a novel technique route to prepare porous polymer beads with controllable pore structure.