Three new Cu(I) π-complexes with 2,5-bis(allylthio)-1,3,4-thiadizole (Bialtia) ([Cu3Cl3(Bialtia)2] (1), [Cu3Cl3(Bialtia)] (2), and [Cu2Cl2(Bialtia)] (3)) are obtained by the alternating current electrochemical synthesis and studied by single crystal X-ray diffraction. A distinctive feature of Bialtia is its ability to coordinate to Cu(I) atoms by nitrogen atoms of the thiadiazole core and two allyl groups. The formation of island inorganic {Cu3Cl3} moieties occurs in 1 through π coordination of two independent Bialtia molecules by three metal atoms. Due to the absence of one Bialtia molecule in 2, inorganic {-Cu3Cl3-} subunits join into infinite chains {[Cu3Cl3(Bialtia)]}n}. The structure of [Cu2Cl2(Bialtia)] (3) contains two Cu(I) atoms with different coordination environments: distorted tetrahedral and trigonal.