A series of mixtures of symmetric metal complexes of C3S22 and C3S4Se2 ligands (C3S22=1.3-dithiole-2-thione-4.5-dithiolate, DMIT; C3S4Se2=1.3-dithiole-2-selone-4-5-dithiolate，DMISE)，LBu4N]2[M(C3S4.4Seo.6)2](M=Ni,1; M-Cu, 2), [Bu4N] [Ni(C3S4.4Seo.6)2]，3，[Bu4N]2[Ni(C3S4.7Seo.3)2], 4, and[Bu4N][Ni(C3S4.7Se0.3)2], 5．have been prepared．Oxidation reactions of 1 with excess iodine afrorded the neutral complex [Ni(C3S4.4Seo.6)2]，6，which exhibited electrical conductivity of 0．29 S cm-1 at 25℃ for a compacted pellet. Single-crystal X-ray analysis of 1 revealed that the anion structure as a whole is planar．Both 3 and 5 form a one-dimensional arrangement through the inter-molecular sulfur-sulfur contacts．The S and Se at the terminal positions of the ligand are disordered．A single-crystal ESR study on[BuN1]2[Cu/Ni(C3S4.4SeO.6)2] demonstrated that the M-S coordination bond in the complex has a strong covalent o-bond character．