The molecule of the title binuclear copper(II) complex, [Cu2(CH3COO)4(C5H5NO)2], occupies a special position on a crystallographic inversion centre; the coordination environment of the CuII atom is slightly distorted square-pyramidal and is made up of four O atoms belonging to four acetate groups in the basal plane with the O atom of pyridine N-oxide ligand in the apical position. The Cu—Cu distance is 2.6376 (6) Å.