Electrolytic reduction of pertechnetate was performed in aqueous solution containing -acceptor ligands. Cyanide and 1,10-phenanthroline were the selected ligands. In both cases, electrolyses produced a cathodic TcO2 deposit and soluble Tc complexes. When cyanide was the ligand, the complexes formed were [Tc (CN)6]5– and [TcO2 (CN)4]3–. When working with the amine, [Tc (phen)3]2+ and another positively charged species were found after reaction. Results are compared with previous studies with amines, and the usefulness of the electrolytic route to obtain Tc complexes is evaluated.