The present study is the first report on the synthesis and characterization of mesoporous composites based on natural rubber (NR) and hexagonal mesoporous silica (HMS). A series of NR/HMS composites were prepared in tetrahydrofuran via an in situ sol-gel process using tetraethylorthosilicate as the silica precursor. The physicochemical properties of the composites were characterized by various techniques. The effects of the gel composition on the structural and textural properties of the NR/HMS composites were investigated. The Fourier-transform infrared spectroscopy (FTIR) and Si-29 magic angle spinning nuclear magnetic resonance (Si-29 MAS NMR) results revealed that the surface silanol groups of NR/HMS composites were covered with NR molecules. The powder X-ray diffraction (XRD) and transmission electron microscopy (TEM) data indicated an expansion of the hexagonal unit cell and channel wall thickness due to the incorporation of NR molecules into the mesoporous structure. NR/HMS composites also possessed nanosized particles (similar to 79.4 nm) as confirmed by scanning electron microscopy (SEM) and particle size distribution analysis. From N-2 adsorption-desorption measurement, the NR/HMS composites possessed a high BET surface area, large pore volume and narrow pore size distribution. Further, they were enhanced hydrophobicity confirmed by H2O adsorption-desorption measurement. In addition, the mechanistic pathway of the NR/HMS composite formation was proposed. (C) 2013 Elsevier B.V. All rights reserved.