Catalyst　performance　is　highly　relevant　to　its　mass　transport　performance.　In　the　present　study,　seven　styrene-codivinylbenzene　polymer　samples　were　synthesized　by　varying　the　amounts　of　crosslinker　and　porogen,　so　as　to　elucidate　mass　transport　mechanism　in　poly　(styrene-co-divinylbenzene)　microspheres　with　hierarchical　pore　structure.　Correspondingly,　pore　structure　parameters　of　seven　samples　were　characterized　by　BET　and　MIP.　By　choosing　toluene　as　probe　molecule,　surface　diffusion　coefficient　and　pore　diffusion　coefficient　of　toluene　inside　the　microspheres　were　measured.　The　experimental　results　indicated　that　both　surface　diffusion　coefficient　and　pore　diffusion　coefficient　increase　with　the　rise　of　the　ratio　of　average　mesopore　diameter　to　average　macropore　diameter　under　a　certain　porosity.　Moreover,　the　rise　of　porosity　results　in　greater　enhancement　of　pore　diffusion　coefficient　than　surface　diffusion　coefficient.　Finally,　sulfonic　acid　groups　were　anchored　onto　polymer　microspheres　to　investigate　the　relative　importance　of　mass　transport　performance　and　catalytic　performance　by　virtue　of　methyl　acetate　hydrolysis.