Nitrite reductase (NiR) is a key enzyme in the anaerobic respiratory pathway of denitrifying bacteria in which nitrite is eventually converted to nitric oxide gas. Copper nitrite reductases catalyse the reaction, NO_2^- + 1e^- + 2H^+ → NO + H_2O. The protein crystallographic study of the nitrite reductase enzyme reveals the locale of the type 1 copper blue-green electron-transfer center and the type 2 copper catalytic center in NiR. Several catalytic mechanisms base on the enzymes and model compounds study are discussed and reveal an important intermediate which may assign to be a {Cu-NO}^(10) complexes. The isolation of the {Cu-NO}^(10) intermediate will help scientist to gain more fundamental knowledge for a deeper understanding of copper nitrite reductase enzymes.