The synthesis procedure for isomeric periodic mesoporous organosilicas with E-configured ethenylene bridges was investigated using the homemade pure E-isomer of 1,2-bis(triethoxysilyl)ethene. The pH, aging temperature and the presence of cosolvents played a key role in obtaining well-ordered mesoporous materials with controllable properties and morphologies. By fine-tuning the reaction mixture acidity, PMOs with high surface areas and pore volumes could be attained. By selecting various alcohols as cosolvents and optimizing the alcohol concentration, PMOs with crystal-like disc shaped, fibrous and spherical particle morphologies were obtained. The synthesis temperature of these ethenylene-bridged PMOs influences the pore size, structure, connectivity and volume.