This work describes the synthesis and structural analysis of the uranium and vanadium complexes [(UO2)(C22H30N6O4)]·MeOH (1) and [(VO)2(O)(C30H36N7O6)]·3MeOH (2) with ligands obtained from the condensation of pyridoxal and triethylenetetramine. The probable mechanism for the formation of imidazoline rings in these complexes is described in some details. Finally, electrochemical and UV–Vis studies of the dinuclear vanadium complex were also carried out in order to determine the variation in the oxidation states of the metallic centers (VO2+/VO3+) in DMSO solution.