The mechanism for the reaction of NCN with OH has been investigated by ab initio molecular orbital and transition-state theory calculations. The potential energy surface (PES) was calculated by the highest level of the modified GAUSSIAN-2 (G2M) method, G2M(CCI). The barrierless association process of OH + NCN → OH⋯NCN (van der Waals, vdw) was also examined at the UCCSD(T)/6-311+G(3df,2p)//B3LYP/6-311+G(d,p) and CASPT2(13,13)/ANO-L//B3LYP/6- 311+G(d,p) levels. The predicted heats of reaction for the production of H + NCNO, HNC + NO, HCN + NO, and N2 + HOC, 7.8, -53.2, -66.9, and -67.7, respectively, are in excellent agreement with the experimental values, 8.2 ± 1.3, -52.3 ±1.7 (or 55.7 ± 1.7), -66.3 ± 0.7, and -68.1 ± 0.7 kcal/mol. The kinetic results indicate that, in the temperature range of 300-1000 K, the formation of trans, trans-HONCN (LM2) is dominant. Over 1000 K, formation of H + NCNO is dominant, while the formation of HCN + NO becomes competitive. The rate constants for the low-energy channels given in units of cm3 molecule-' s-1 can be represented by the following: k1(LM2) = 1.51 × 10 15T-8.72 exp(-2531/7) at 300-1500 K in 760 Torr N 2; k2(H+NCNO) = 5.54 × 10 -147- 097 exp(-3669/T) and k3(HCN+NO) = 7.82 × 10 -14T0.44 exp(-2013/T) at 300-2500 K, with the total rate constant of kt = 3.18 × 10 27-4.63 exp(-740/T), 300-1000 K, and kt = 2.53 × 10 -14T1-13 exp(-489/T) in the temperature range of 1200-2500 K. These results are recommended for combustion modeling applications.