The synthesis of novel periodic mesoporous organosilica (PMO) materials incorporating a mixture of functional monomers (cis- and trans-stilbene-based) and structural monomers has been accomplished. EDX analysis of these materials in combination with HAADF imaging of OsO4-stained samples reveals a homogeneous distribution of trans-olefin within the co-condensed aromatic organosilica matrix. Ozonolysis of the functional component demonstrates the significant potential of this material for further modification.