In this study, a series of luminescent mesoporous hybrid organometallo-silica materials were successfully prepared via sol–gel coordination chemistry. The condensation of organometallic Ir(III) and Pt(II) complexes containing a 2-(diphenylphosphino)ethyltriethoxysilane (PPETS) ligand with the silica precursor (TEOS) yielded hybrid materials with homogeneous metal incorporation in the silica network and excellent luminescent and textural properties. All the reactions were carried out at room temperature and in the absence of a surfactant. Powders and transparent gels were prepared by adjusting the synthesis conditions and amounts of incorporated organometallic complex, yielding very stable emissive materials.