This study is the first report on synthesis, characterization and catalytic application of propylsulfonic acid-functionalized mesoporous composites based on natural rubber (NR) and hexagonal mesoporous silica (HMS). In comparison with propylsulfonic acid-functionalized HMS (HMS-SO3H), a series of NR/HMS-SO3H composites were prepared via an in situ sol gel process using tetrahydrofuran as the synthesis media. Tetraethylorthosilicate as the silica source, was simultaneously condensed with 3-mercaptopropyltrimethoxysilane in a solution of NR followed by oxidation with hydrogen peroxide to achieve the mesoporous composites containing propylsulfonic acid groups. Fourier-transform infrared spectroscopy and Si-29 MAS nuclear magnetic resonance spectroscopy results verified that the silica surfaces of the NR/HMS-SO3H composites were functionalized with propylsulfonic acid groups and covered with NR molecules. After the incorporation of NR and organo-functional group into HMS, the hexagonal mesostructure remained intact concomitantly with an increased framework wall thickness and unit cell size, as evidenced by the X-ray powder diffraction analysis. Scanning electron microscopy analysis indicated a high interparticle porosity of NR/HMS-SO3H composites. The textural properties of NR/HMS-SO3H were affected by the amount of MPTMS loading to a smaller extent than that of HMS-SO3H. NR/HMS-SO3H exhibited higher hydrophobicity than HMS-SO3H, as revealed by H2O adsorption-desorption measurements. Moreover, the NR/HMS-SO3H catalysts possessed a superior specific activity to HMS-SO3H in the esterification of lauric acid with ethanol, resulting in a higher conversion level. (C) 2014 Elsevier B.V. All rights reserved.