The pentacyanoferrate(II)–ammonia–nitrite system was subjected to a kinetic and mechanistic study as a function of NH₃ and NO₂^– concentration, pH, temperature and pressure. A detailed study was performed on the formation of [Fe^II(CN)₅(NO)]^2– in the system consisting of NO₂^– and [Fe^II(CN)₅L]^3– (L = H₂O or NH₃). Two equilibria were taken into consideration, viz. the pH dependent aquation of the ammine complex, and the transformation of the nitro into the nitrosyl complex. Based on the reported activation parameters, the substitution of water or ammonia in [Fe^II(CN)₅L]^3– (L = H₂O or NH₃) by nitrite follows a limiting dissociative mechanism. The reaction of [Fe^II(CN)₅(NO)]^2– with ammonia leading to the formation of dinitrogen was investigated in a more qualitative way, and found to depend strongly on pH with a maximum nitrogen yield at a pH of ca. 10.5. The trend was accounted for on the basis that the process involves nucleophilic attack of NH₃ on the N (NO) atom in [Fe^II(CN)₅(NO)]^2–. This reaction was found to be the rate-limiting step in the catalytic cycle occurring in this system and leading to the overall reduction of NO_x to dinitrogen.