We employed two pairs of new in-situ-generated chiral amino acid tetrazole ligands in constructing homochiral Zn(II) coordination compounds: [Zn(tzet)] (la for (S)-tzet and 1b for (R)-tzet, H(2)tzet = N42-(1H-tetrazol-5'ypethyl]tryptophan) and [Zn(tzep)(H20)2].H2O (2a for (S)tzep and 2b for (R)-tzep, H2tzep = N-[2-(1H-tetrazol-5yl)ethyl]proline), which were hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction. Structural analysis reveals that 1 features a 2D hornochiral framework generated by both tetrazolate and carboxylate bridges in tzet2 ligands. The isolated structure of 2 is stabilized by extensive hydrogen bonds, which leads to formation of a supramolecular 2D architecture. The absolute.: configuration induced at the nitrogen atoms of 1 and 2 is strictly related to the neighboring chiral carbon atoms by hydrogen, bond interactions. To further investigate their chirality, the combined experimental and theoretical analyses of circular dichroism spectra reveal the absolute configurations and nature of the Cotton effects. Solid-state excitation and emission spectra for 1 and 2 at room temperature were investigated with relevant density of states calculation, and tunable photoluminescence emission of 1 under different excitation wavelengths was discussed. As nitrogen rich tetrazolate compounds, 1 and 2 possess higher enthalpies of combustion and may serve as a new family of promising energetic materials.