By means of alternating current electrochemical technique a new tetranuclear crystalline copper(I) complex [Cu I 4 (L − ) 4 ] (L − –allyl(5-phenyl-1,3,4-thiadiazol-2-yl)azanide ion) has been obtained and characterized by X-ray single crystal diffraction (Sp. gr. I4 1 /a) and Raman spectroscopy. The metal center adopts linear arrangement, composed of one thiadiazole N atom from the one L − anion and one azanide N atom of the other L − ligand. A bridged Cu atoms stitch four L − ligands into the firstly observed tetranuclear copper(I) azanide complex with intramolecular Cu(I)⋯Cu(I) interactions at the distance of 2.7451(6)Å. Molecular structure and Raman spectrum of the compound have been computed using the DFT B3LYP methodology and the cc-pVDZ basis set. The results are compared with the experimental data obtained. Spectrum calculation followed by normalization to the most intensive peak allowed providing detailed vibrational band assignment.