Copper(II) complexes were prepared with the new N2S(thioether) ligand 2-methylthio-N-(2-pyridylmethyl)acetamide (2-HLN2S). [Cu(2-L-N2S)Cl(MeOH)], which formed in the presence of excess triethylamine, is a distorted square pyramidal complex containing the ligand with the amide nitrogen deprotonated. The structurally analogous complex, [Cu(2-HLN2S)Cl-2], which formed in the absence of triethylamine, contains 2-HLN2S in the tautomeric imidic acid form. Neutral copper(II) N2S(thioether)S(thiolate) species were generated by addition of alkyl or aromatic thiolates to [Cu(2-L-N2S)Cl(MeOH)] and an unusual decomposition pathway was discovered.