Hole-transporting framework is formed by surfactant-templated sol-gel polycondensation of an electroactive phenylenevinylene-based organosilane precursor. Molecular geometry of the three-armed precursor contributes to both formation of periodic mesostructures and introduction of hole conductivity in the organosilica hybrids. Electroactive organosilicas with mesopores and large surface areas have great potentials for novel photovoltaic and photocatalytic systems.