Three functionalized ligands, S(−)-N-(pyridin-2-ylmethyl)lactamide (pml), S(−)-N-(2-dimethylaminoethyl)lactamide (dmael) and S(−)-N-(3-dimethylaminopropyl)lactamide (dmapl), were synthesized by the aminolysis of S(−)-methyl lactate with the corresponding primary amines. Their protonation constants and the stability constants of the chelates formed with copper(II) were determined by potentiometry. In all cases, we detected the formation of CuLH−1+, CuLH−2 and CuLH−3− species (L = free ligand). The copper(II) complexes prepared in the solid state were characterized by IR and UV-visible spectroscopies. The crystal structure of [Cu(pmlH−1)X] (X = Cl, Br) shows that copper(II) is bound to the pyridyl and the deprotonated amidic nitrogen atoms, as well as to the oxygen atom of the hydroxyl group, which leads to a mono-chelated compound. The geometry around Cu2+ is square pyramidal.