Two copper(II) complexes, [CuL3](ClO4)2 bearing one N-CH2CH2CONH2 group as well as one N-CH2CH2CN group and [CuL4](ClO4)2 bearing two N-CH2CH2CONH2 groups, have been prepared by the selective hydrolysis of [CuL2](ClO4)2 (L2 = C-meso-1,8-bis(cyanoethyl)-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane). The complex [CuL5](ClO4)2 bearing one N-CH2CH2C(=NH)OCH3 and one N-CH2CH2CN groups has been prepared as the major product from the reaction of [CuL2](ClO4)2 with methanol in the presence of triethylamine. In acidic aqueous solution, the N-CH2CH2C(=NH)OCH3 group of [CuL5](ClO4)2 undergoes hydrolysis to yield [CuL6](ClO4)2 bearing both N-CH2CH2COOCH3 and N-CH2CH2CN groups. The crystal structure of [CuL5](ClO4)2 shows that the complex has a slightly distorted square-pyramidal coordination polyhedron with an apical Cu-N (N-CH2CH2C(=NH)OCH3 group) bond. The apical Cu-N bond distance (2.269(3) A) is ca. 0.06 A longer than the apical Cu-O (N-CH2CH2CONH2 group) bond of [CuL4](ClO4)2. The pendant amide group of [CuL3](ClO4)2 is involved in coordination. The carboxylic ester group of [CuL6](ClO4)2 is also coordinated to the metal ion in various solvents but is removed from the coordination sphere in the solid state.