The reaction of phenyl 2-pyridyl ketoxime (PhPyCNOH) with Cu(NO 3 ) 2 ·3H 2 O in methanol results in the chiral trinuclear complex [Cu 3 (OH)(PhPyCNO) 3 (NO 3 ) (CH 3 OH)]·(NO 3 ) (1), which has been characterized by elemental analysis, IR spectra and single-crystal X-ray diffraction. The structure of 1 exhibits a triangle of Cu(II) ions, centered by a triply bridging hydroxo ligand and with three edge-bridging oximate groups from the three PhPyCNO − ions. Preliminary variable-temperature magnetic susceptibility studies reveal an antiferromagnetically-coupled system showing antisymmetric exchange. Complex 1 crystallizes in an acentric space group (P2 1 ) that belongs to a polar point group, which displays second harmonic generation response and ferroelectric behavior, and provides a new strategy for designing functional coordination complexes.