Periodic mesoporous organosilica (PMO) is a special type of ordered mesoporous silica, in which organic moieties are integrated into the silica framework to form hybrid organic–inorganic material. In this work, we successfully incorporate T-type large sized melamine based triorganosilsesquioxane as organic linker in the periodic mesoporous organosilica. Melamine-bridged PMOs were prepared with high reproducibility by co-condensation using N2,N4,N6-tris(3-(triethoxysilyl) propyl)-1,3,5-triazine-2,4,6-triamine (TBTS) and sodium metasilicate in the presence of poly(ethylene oxide)–poly(propylene oxide)–poly(ethylene oxide) triblock copolymer (Pluronic P123, EO 20 PO 70 EO 20 , Aldrich) at high acidic concentration. The resulted melamine PMO had well-ordered p6mm hexagonal mesostructure and played a role as an efficient catalyst for carbon dioxide activation in the coupling of propylene oxide with CO 2 . The adsorption behavior of carbon dioxide at the GGA-RPBE level of DFT was explored as a first step towards new mechanistic pathways for CO 2 activation over metal-free catalyst.