Metal bis-dithiolene complexes have aroused more and more interest over the past decades due to their potential applications as precursors for electrical conductors and superconductors; the optical properties of these compounds are also very interesting. For example, in 1972 Drexhage and co-workers discovered that transition metal dithiolene complexes are very stable to intense irradiation in the near-infrared region and are particularly suitable for Q-switching lasers. Recently, more and more symmetrical bis-dithiolene complexes with third-order optical nonlinearity or optical limiting effects have been explored. Because of the large values of their third-order nonlinear susceptibility and negative molecular first hyperpolarizability, unsymmetrical dithiolene complexes have also become promising candidates for nonlinear optical materials [1]. We have received mixed-ligand complexes on the basis of 1,3-dithiole-2-thione-4,5-dithiolate (C3S5 2-, dmit) of structure [M(dmit)(Am)n], where n=1, 2, M - Zn, Cu, Ni; Am - phen, en. The structure of complexes is confirmed by methods of the elemental analysis, XRD and also IR-and UV-spectroscopy. For example, the complex [Zn(dmit)(phen)2] has a quasi-octahedral structure. Bond lengths of Zn-S (2.43 Å) and Zn-N (2.21 Å) are in the same range, as in complex [Zn(dmid) (phen)2] [2]. In an electronic absorption spectrum two intensive bands are observed at 310 nm (ε = 13000) and 504 nm (ε = 7370). Being based on the literature [1,2], first of them can be attributed to the intraligand excitation [π(phen) → π*(phen)], and the second - to similar π→π* excitation of coordinated dmit. According to such interpretation, the emission spectrum of complex (lines at 393 and 434 nanometers), arising at an irradiation the laser with wave-length 337 nanometers, can be assigned to the π*→π transition from the coordinated molecule phen to ligand dmit.