Five CuII Schiff-base complexes, three mononuclear {[Cu(rslysH)·(H2O)2]·2H2O·ClO4 (1); [Cu(rslysH)Cl] (2); [Cu(slysH)(H2O)Cl] (3) rslys and slys = 6-amino-2-[(2-hydroxybenzylidene)amino]hexanoate} and two dinuclear {[Cu2(rslysH)2(CH3OH)2]·(H2O)2(NO3)2 (4); [Cu2(slysH)2(NO3)2]·(H2O)3 (5)}, are reported herein. These complexes have been synthesized via a facile “one-pot” method in which the D/L- and L-lysine Schiff-base ligands are generated in situ. Various spectroscopic techniques and single-crystal X-ray diffraction were used in compound characterization. The X-ray diffraction studies revealed that complexes 1–3 are mononuclear; further, 4 and 5 are dinuclear in which two CuII centers are phenolate-bridged. Complexes 1, 2 and 3 are structurally similar, according to the nuclearity and the coordination environment around the metal center involving a tridentate D- or L-lysine-derived Schiff-base ligand. But the crystallographic packing is different, owing to the different counterions and number of solvent molecules present in the crystals. Compounds 1 and 2 are racemic due to the co-existence of chiral D- and L-lysine-based Schiff-base ligands. These copper(II) complexes give 2-D hydrogen-bonded networks and are racemic overall. Compound 3 is chiral, containing only the L-lysine-derived ligand in which a cylindrical 1-D hydrogen-bonded structure is observed in the solid state. Both 4 (achiral) and 5 (chiral) reveal 3-D hydrogen-bonded networks. A strong antiferromagnetic coupling interaction was observed by variable-temperature magnetic susceptibility measurements; this interaction is likely mediated through the phenolate bridge between the two CuII centers in 4 and 5.