The synthesis of a new sodium perchlorate adduct (1:3) with a copper(II) "ligand-complex" is reported in which 2-hydroxyacetophenone acts as a guest. The adduct is tetranuclear of formula {[(CuL)3Na]ClO 4}2·C8O2H8· 0.5CH3CN (1). The ligand is the tetradentate di-Schiff base of 1,3-propanediamines and o-hydroxyacetophenone (H2L). The complex has been characterized by X-ray single crystal structure analysis. In the structure, the sodium cation has a six-coordinate distorted octahedral environment being bonded to six oxygen atoms from three Schiff base complexes. The complex exhibits reversible reductive (CuII/CuI; Epc, -0.914 V) and oxidative (CuII/CuIII; Epa, +1.060 V respectively) responses in cyclic voltammetry. The generated Cu I species for the complex is unstable and undergoes disproportionation to Cu0 and Cu2+.