The synthesis of periodic mesoporous organosilicas (PMOs) in the confinement of porous anodic alumina membranes (AAMs) was successfully achieved through a modified evaporation-induced self-assembly (EISA) process. 1,3,5-Tris(4-triethoxysilylstyryl)benzene, (a three-armed oligo(phenylenevinylene) organosilane compound, abbr. 3a-OPV), the precursor of the first reported charge-conducting PMO, was used as an organosilica source. Triblock-copolymers Pluronic F127 (EO 106 PO 70 EO 106 ) or F108 (EO 132 PO 50 EO 132 ) were used as structure directing agents. The block-copolymer F127 led to a 2D-hexagonal circular mesostructure within the AAM channels and the block copolymer Pluronic F108 resulted in a mesophase with a body-centered cubic (Im 3m) structure. Compared to the previously reported 3a-OPV-PMO film, the resulting hierarchical PMO/AAM systems have improved features, that is, the synthesized PMOs have a pore size of around 10 nm and the compounds are found to be stable against thermal treatment at temperatures of up to 200 C and they are also stable in the electron beam of the electron microscope. Additionally, both of the resulting hierarchical mesoporous composites show fluorescence in the visible region due to the strongly interacting phenylenevinylene chromophores in the PMO frameworks.