Ordered mesoporous, highly luminescent SiO2 particles have been synthesized by spray pyrolysis from solutions containing tetraethylorthosilicate (TEOS), Eu(NO3)3.6H2O, and cetyltrimethylammonium bromide (CTAB) as structure-directing agents. The 1,10-phenantroline (Phen) molecules were coordinated in a post-synthesis step by a simple wet impregnation method. In addition, other matrices were also prepared by the encapsulation of europium complex Eu(fod)3 (where fod = 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedionato) into mesoporous silica, and then the Phen molecules were encapsulated by different impregnation steps, after which the luminescence properties were investigated. The obtained materials were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), powder x-ray diffraction (XRD) and Fourier transform infrared (FTIR) spectroscopy. Powders with polydisperse spherical grains were obtained, displaying an ordered hexagonal array of mesochannels. Luminescence results revealed that Phen molecules had been successfully coordinated as an additional ligand in the Eu(fod)3 complex into the channels of the mesoporous particles without disrupting the structure.