Synergistic properties in hybrid materials can emerge if the inorganic matrix has an electronic influence on the organic constituents and vice versa. This paper describes the drastic effect of SiO2 in periodically ordered mesoporous organosilica materials (PMOs) on ethylene groups. A sophisticated, in situ solid-state NMR spectroscopy study showed that the ozonolysis of ethylene groups follows an entirely different mechanism than is normal for organic, molecular groups. Ultimately, this leads to the topotactic transformation of the PMO material. Only if silicon is not in the alpha position to the double bond does it became possible to establish a new method to functionalize PMOs materials: the targeted scission of the ethylene group and the creation of functionalized pockets inside the pore walls of the mesoporous solid.