Four novel luminescent ruthenium(II) complexes of general formulas [RuH(X)(MeCN)(CO)(PPh3)2] and [Ru(X)2(MeCN)(PPh3)2] (where X = N3−, NCS−) were synthesized and characterized by IR, NMR, UV-Vis spectroscopy, X-ray crystallography and electrochemical studies. The emission properties of the complexes were studied at ambient and low temperatures. The quantum yields of fluorescence, lifetimes and nature of the excited states were discussed based on molecular properties. To elucidate the structural, spectroscopic and bonding properties of obtained complexes, calculations at the DFT level were undertaken. The received azide and thiocyanate analogs of precursor complexes, [RuHCl(CO)(PPh3)3] and [RuCl2(PPh3)3], exhibit luminescence properties at ambient temperature as well as at the temperature of liquid nitrogen (77 K). The carefully studies of the emissive excited states nature, play an important role in understanding the luminescent properties of phosphine ruthenium(II) complexes, which are poorly characterized in that field. The emission spectra, the decay times, the quantum yields of luminescence in correlation with electrochemistry and quantum-mechanical calculations indicate that, in the creation of excited states of the complexes engaged are both the metal d orbitals and pseudohalide ligands orbitals.