Reaction of the potassium salt of N-thiophosphorylthiobenzamide PhC(S)NHP(S)(OiPr)(2) (HL) with CuI in aqueous EtOH leads to the tetranuclear [Cu(4)L(4)] and the polynuclear [KCuL(2)](n) complexes, while the same reactions using the lithium or sodium salts of HL exclusively lead to the tetramer [Cu(4)L(4)]. Reaction of KL with the mixture of CuI and 2,2'-bipyridine (bpy) or 1,10-phenanthroline (phen) leads to the mononuclear complexes [Cu(bpy)L] and [Cu(phen)L]. The same complexes were obtained by the reaction of [Cu(4)L(4)] with bpy or phen.