A new postsynthetic method has been developed for sulfonic acid functionalization of hybrid periodic mesoporous organosilica (PMO) materials containing carbon-carbon double bonds (-C═C-) located in mesoporous wall structures. Hexagonal mesoporous ethenylene-silicas (HME) with different pore sizes were synthesized by using P123, Brij76, and Brij56 surfactants and investigated for postsynthetic functionalization. The present functionalization strategy involves epoxidation of double bonds at -5 °C followed by conversion of the resulting epoxide with bisulfite ions at 65 °C and involves neither the use of well-known mercaptol/H2O2 nor harsh concentrated H2SO4 reagents during the course of -C═C- functionalization. The epoxidation step plays a crucial role in determining the amount of -SO3H groups functionalized onto the silica support which is optimized with respect to different synthesis parameters. The ethenylene-silicas both before and after chemical modification were thoroughly characterized by powder XRD, TEM, N2 adsorption, Raman spectroscopy, 13C and 29Si MAS NMR, and catalytic test reactions. X-ray powder diffraction measurements and sorption data indicated that the mesostructure was intact during the postsynthetic chemical modification. Raman spectra exhibited two strong bands at 1567 and 1290 cm(-1) for ethenylene-silica attributed to -C═C and -C-H stretching vibrations, respectively; whereas after epoxidation and sulfonation, new bands were observed at 1215 and 1035 cm(-1) corresponding to the epoxide and -SO3 stretching vibrations, respectively. 13C CP MAS NMR of surfactant extracted ethenylene-silica exhibits a signal at 146 ppm along with signals at 16.4 and 17.4 ppm. The appearance of new signals at 47.7 and 46.5 ppm is attributed to carbon atom with ≡C-OH and ≡C-SO3H groups, respectively. 29Si MAS NMR spectra exclusively showed T2 and T3 species at -73 and -82 ppm, respectively both before and after chemical modification and negligible amount of Q3 or Q4 species confirms the stability of Si-C bonds during the functionalization. The sulfonic acid-functionalized mesoporous ethenylene-silicas show high catalytic activity in esterification of acetic acid with ethanol under liquid-phase reaction conditions.