The reactions of (S)-3-cyanophenylalanine with NaN3 in the presence of H2O and Lewis acids (ZnCl2 and CdCl2) afford two unprecedented 3D homochiral networks, mono[(S)-5-(3-tetrazoyl)-phenylalaninato]zinc(II) (1) and mono[(S)-5-(3-tetrazoyl)-phenylalaninato]cadmium(II) monoaqua(II) (2), respectively. The two compounds are isostructural with noninterpenetrated SrAl2 topology. The structure of these coordination polymers gives new insight into Sharpless' reaction of chiral 5-substituted 1H-tetrazole and homochiral supramolecular array constructions.