Mesostructured and mesoporous materials are emerging as a new class of optical materials. However, their synthesis is nontrivial. In this work, periodic mesostructured metal complex-containing silicas of MCM- and SBA-type bearing homogeneously distributed photoluminescent tri(8-quinolinolato)aluminum inside the channel walls (denoted as Alq(3)@PMO-MCM and Alq(3)@PMO-SBA, respectively) have been achieved via one-pot co-assembling of inorganic/surfactant/optically active species. A comprehensive multianalytical characterization of the structural and optical properties demonstrates that both Alq(3)@PMO-MCM and Alq(3)@PMO-SBA series gainfully combine the photoluminescent properties of Alq(3) with the porous features of PMOs. Regularly arranged pores provide high surface area to disperse optically active components well and render Alq(3)-containing PMOs promising materials for optoelectronic applications. (C) 2013 Published by Elsevier Inc.