The exchange reactions of 4,6-di-tert-butylpyrocatechols containing in position 3 different N‑aryliminomethyl groups (aryl is p-halophenyl; halogen is fluorine (I), chlorine (II), bromine (III), and iodine (IV); p-tolyl (V)) with copper(II) acetate in a molar ratio of 2 : 1 afford planar square copper(II) o‑iminophenolate complexes of the general formula [(R-CatH)2Cu], where R is the aryl substituent in the Ar–N=CH group. The molecular structures of complexes I, III, and V in the crystalline state are determined by X-ray diffraction (XRD) (CIF files CCDC nos. 2227448 (I), 2226727 (III), and 2227449 (V)). The electrochemical properties of compounds I–V are studied by cyclic voltammetry.