Two pairs of chiral Zn(II) complexes, Zn((−)-L1)Cl2 ((−)-1) and Zn((+)-L1)Cl2 ((+)-1), Zn((−)-L2)Cl2 ((−)-2) and Zn((+)-L2)Cl2 ((+)-2), [(−)-L1=(−)-4,5-pinene bipyridine, (+)-L1=(+)-4,5-pinene bipyridine, (−)-L2=(−)-‘dipineno’-[4,5:4″,5″]-fused 2,2′:6′,2″-terpyridine, (+)-L2=(+)-‘dipineno’-[4,5:4″,5″]-fused 2,2′:6′,2″-terpyridine] were facilely prepared by the complexation of ligand L with chiral polypyridine ligands with ZnCl2. Their structures were characterized by single crystal X-ray diffraction and electronic circular dichroism (CD) spectra. The central Zn(II) nucleus in (−)-1 is surrounded in a four-coordinate tetrahedral geometry, while the coordination polyhedron of the Zn(II) ion in (−)-2 can be described as a significantly distorted square-pyramidal. Due to different coordination modes and crystal space groups, complexes (−)-1 and (−)-2 show distinct ferroelectric behaviors and nonlinear optical properties, while both of them are emissive at room temperature, which may give a guidance for designing molecule-based multifunctional materials with diverse coordination configurations.