Novel and efficient mesoporous polydivinylbenzene (PDVB) based solid strong acid (PDVB-SO3H-SO2CF3) has been successfully prepared by grafting of strong electron withdrawing group of -SO2CF3 onto the network of performed mesoporous solid acid of PDVB-SO3H, which could be synthesized from sulfonation of superhydrophobic mesoporous PDVB or copolymerization of DVB with sodium p-styrene sulfonate. Characterizations of N-2 sorption isotherms, TG curves and contact angle tests show that PDVB-SO3H-SO2CF3 has large Brunauer-Emmett-Teller (BET) surface area, superior thermal stability, good hydrophobicity and oleophilicity. Solid P-31 NMR spectra and NH3-TPD curves show that the Bronsted acidic site in PDVB-SO3H-SO2CF3 has been significantly enhanced and rather homogeneously distributed when compared with that of PDVB-SO3H. Catalytic tests show that PDVB-SO3H-SO2CF3 exhibits excellent catalytic activities and good recyclability in biomass transformation toward transesterification to biodiesel and depolymerization of crystalline cellulose to sugars when compared with those of PDVB-SO3 H, solid strong acids of SO4/ZrO2 and Nafion NR50. The excellent catalytic activity and good recyclability of PDVB-SO3H-SO2CF3 result from its unique characters such as large surface area, ultra strong acid strength, adjustable hydrophobic-oleophilic and stable network. (C) 2013 Elsevier B.V. All rights reserved.