Inorganic–organic hybrid membrane materials always exhibit high pervaporation performance for organic azeotropic mixtures. Here, MCM‐41 silica spheres were modified and embedded into polydimethylsiloxane, and a new filled membrane was obtained. The membrane was used in dimethylcarbonate (DMC) removal from DMC/methanol azeotropic mixture by pervaporation. The effect of membrane preparation parameters including modified MCM‐41 silica spheres loading, solvent concentration, and feed temperature on pervaporation properties was systematically studied. The results showed that separation factor and total flux of the filled membranes could be increased simultaneously. Additionally, the sorption and diffusion selectivity of the filled membranes were measured and discussed. The results demonstrated that diffusion selectivity was greatly enhanced by incorporating. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013