A photoactive, hexagonally structured mesoporous material (Tyl-MCM41) is produced through co-hydrolysis of SiO(2) and a trialkoxysilane-functionalized trityl cation as photoactive species. The formation of the corresponding triphenylmethanol precursor in the material is confirmed by spectroscopic techniques. The hybrid material has an ordered structure with a narrow pore size distribution typical of ordered mesoporous MCM-41-type materials. The triarylcarbinol molecules incorporated into this hybrid structure (Triphol-MCM41) generate trityl cations under acidic conditions, which are photoactive and able to promote the photosensitized dimerization of 1,3-cyclohexadiene in a heterogeneous solid-liquid system. The material is stable and can be recycled without loss of the photochemical activity.