As a powerful macrocyclic host molecule with unique conformation and cavity structure that are fine-tuned by the bridging nitrogen atoms, methylazacalix[4]pyridine (MACP-4) has been shown to selectively recognize Zn2+ and form stable Zn(II)-MACP-4 complexes both in solid state and solution with an association constant up to 5.97 (logK s). The molecular recognition of Zn(II)-MACP-4 complexes towards various amino acids and anions with different geometry was investigated by using the spectral titration methods and X-ray analysis. The Zn(II)-MACP-4 complex was found to recognize the 17 amino acids tested with the association constant up to 3.97 (logK s). On the other hand, the Zn(II)-MACP-4 complex selectively interacted with anions and the maximum association constant of 3.9 (logK s) was obtained.