A novel optoelectroactive system based on an oriented periodic mesoporous organosilica (PMO) film has been developed. A tetra-substituted porphyrin silsesquioxane was designed as a precursor, and the porphyrin macrocycles were covalently incorporated into the organosilica framework without adding additional silica sources, using an evaporation-induced self-assembly process. The synthesized PMO film has a face-centered orthorhombic porous structure with a 15 nm pore diameter. This large pore size enables the inclusion of electron-conducting species such as [6,6]-phenyl C61 butyric acid methyl ester in the periodic mesopores. Optoelectronic measurements on the resulting interpenetrating donor-acceptor systems demonstrate the light-induced charge generation capability and hole-conducting property of the novel porphyrin-based PMO film, indicating the potential of PMO materials as a basis for optoelectroactive systems.