Five new Cu(II) complexes [Cu(psa)(phen)] · 3H 2O ( 1), [Cu(psa)(2bpy)] · 0.5H 2O ( 2), [Cu(psa)(2bpy)(H 2O)] · 3H 2O ( 3), [Cu(psa)(4bpy)] · H 2O ( 4), and [Cu(psa) 0.5(N 3)(2bpy)] ( 5) (H 2psa = phenylsuccinic acid, phen = 1,10-phenanthroline, 2bpy = 2,2′-bipyridine, and 4bpy = 4,4′-bipyridine) were obtained under solvothermal conditions and characterized by single-crystal X-ray diffraction. Complexes 2 and 3 were formed by one-pot reaction. In complex 2, Cu(II) ion is four-coordinated and locates at a slightly distorted square center. In complex 3, the coordinated water molecule occupies the axial site of Cu(II) ion forming a tetragonal pyramid geometry. Complexes 1 and 3 are of 1D chain structures, and extended into 2D supramolecular network by hydrogen bonds. Complex 2 is of zipper structure, and further assembled into 2D supramolecular network by hydrogen bonds and π–π stacking interactions. Complex 4 is a 3D CdSO 4-like structure with twofold interpenetration, while complex 5 is a dinuclear compound. The different structures of complexes 1– 5 can be attributed to using the auxiliary ligands, indicating an important role of the auxiliary ligands in assembly and structure of the title complexes.