A series of new organic ligands (5Z,5Z′)-2,2′-(alkane-α,ω-diyldiselenyl)-bis-5-(2-pyridylmethylene)-3,5-dihydro-4H-imidazol-4-ones (L) consisting of two 5-(2-pyridylmethylene)-3,5-dihydro-4H-imidazol-4-one units linked with polymethylene chains of various lengths (n = 2–10, where n is the number of CH₂ units) have been synthesized. The reactions of these ligands with CuCl₂·2H₂O and CuClO₄·6H₂O gave Cu²⁺ or Cu¹⁺ containing mono- and binuclear complexes with Cu₂LCl_x (x = 2–4) or CuL(ClO₄)_y (y = 1, 2) composition. It was shown that the agents reducing Cu²⁺ to Cu¹⁺ in the course of complex formation can be both a ligand and an organic solvent in which the reaction is carried out. This fundamentally distinguishes the selenium-containing ligands L from their previously described sulfur analogs, which by themselves are not capable of reducing Cu²⁺ during complexation under the same conditions. A higher cytotoxicity and reasonable selectivity to cancer cell lines for synthesized complexes of selenium-containing ligands was shown; unlike sulfur analogs, ligands L themselves demonstrate a high cytotoxicity, comparable in some cases to the toxicity of copper-containing complexes.