Probes using luminescent transition metal complexes for determination of contents and conditions of environment are very promising. This work deals with the investigation of spectral properties of highly luminescent Ru(II) polypyridil complexes with such ligands as 2,2'-bipyridine, 1,10-phenanthroline, 4,7-diphenyl-1, 10-phenanthroline and their substitution analogues immobilized on porous glass surface. The object under investigation possesses a number of desirable features, since it combines luminescence properties of metal-ligand complexes with mechanical and technological advantages associated with employment of porous glass matrix. Emission of Ru(II) polypyridil complexes is typically dominated by a series of lowlying metal to ligand charge-transfer excited states. Luminescence spectra reveal wide structureless band with maxima ranging from 605 nm for Ru-tris-1,10-phenanthroline to 645 nm for Ru-4,7-diphenyl-1, 10-phenanthroline. The luminescence band shape and placement are practically independent of excitation wavelength. The radiative transition from the excited states is strongly influenced by external factors, such as presence of a quencher or temperature variations. The experiments revealed nonmonotonous character of temperature dependence of luminescence intensity. While the compositions are heated, the original luminescence quantum yield downfall in a temperature range up to 110 K is reversed and there appear to be an interval (110 - 200 K for Ru-4,7-diphenyl-1, 10-phenanthroline), where quantum yield rises, reaching maximum at 200 K. Subsequent heating up to 370 K is followed by renewal of quenching. This phenomena could be explained taking into account porous matrix inhomogeneity, leading to the existence of complexes with different orientation as to the matrix surface.