Cu-containing nitrite reductase is a homotrimer in which a ca. 36 kDa monomer contains each of type 1 Cu (two His, Cys, and Met ligands) and type 2 Cu (three His and solvent ligands). Type 1 Cu receives one electron from an electron donor and transfers it to the reaction center, type 2 Cu. The distance between the two Cu atoms bound by the Cys-His sequence segment is 12.6 A. The intramolecular electron transfer from type 1 Cu to type 2 Cu occurs probably through this segment. The noncoordinated Asp and His residues around type 2 Cu play important roles in both the electron-transfer and the catalytic processes.