Five new homochiral supramolecular networks of complexes, namely, [Ni(L)2(H2O)6]·2H2O (1), [Cu(L)2(H2O)3]·H2O (2), [Zn(L)2(H2O)2]·H2O (3), [Cd(L)2(H2O)2]·H2O (4) and [Cd(L)2(H2O)]n (5) [L = (S)-naproxen anion], have been prepared and structurally characterized by single crystal X-ray diffraction, powder X-ray diffraction (PXRD), elemental analysis, thermogravimetric analysis (TGA), and infrared (IR) spectroscopy. Complex 1 crystallizes in the space group P1, which is a mononuclear structure. In 1, there exists a variety of hydrogen bonding interactions, which further extend to a 3D supramolecular architecture. Complexes 2–4 crystallize in the space group C2, and all of them exhibit mononuclear structures. Intermolecular hydrogen bonding and C–H⋯π interactions are observed in complexes 2–4. Complex 5 crystallizes in the space group Cc, showing a one-dimensional chain structure. Hydrogen bonding (O–H⋯O) and weak stacking interactions (C–H⋯π) are also found. All of the complexes display significant ferroelectric properties and second harmonic generation response. Additionally, the photoluminescence spectra of complexes 3–5 have also been discussed.