Efficient and stable solid acid catalysts, sulfonic groups functional swelling mesoporous polydivinylbenzenes (PDVB-x-SO(3)Hs), were synthesized from sulfonation of swelling mesoporous polydivinylbenzenes (PDVB-xs) by chlorosulfonic acid in CH2Cl2. Nitrogen adsorption-desorption isotherms showed that PDVB-x-SO(3)Hs have high surface area and abundant mesoporosity. Elemental analysis and acid-base titration techniques showed that PDVB-x-SO(3)Hs have high concentration of sulfonic groups. Esterifications of acetic acid with cyclohexanol, hexanoic acid with ethanol, lauric acid with ethanol and acylation of anisole with acetyl chloride showed that PDVB-x-SO(3)Hs are more active than arenesulfonic, propylsulfonic groups functional mesoporous silicas (SBA-15-Ar-SO3H, SBA-15-Pr-SO3H) and strongly acidic ion-exchange resin (Amberlyst 15). The superior performance of PDVB-x-SO(3)Hs is attributed to their unique features including large surface area, abundance of mesoporosity as well as high content of sulfonic groups. (C) 2010 Elsevier Inc. All rights reserved.