Based on the information from GC-MS on-line measurement and thermodynamic analysis, the reaction network of gas-phase hydroxylation of benzene with nitrous oxide over Fe-ZSM-5 zeolite was systematically investigated. The main reactions and side reactions were identified, and a kinetic reaction network was proposed as follows: benzene+N2O→phenol→CO/CO2. According to the mechanism, the experimental results were interpreted reasonably. The hydroxylation kinetic experiments were carried out in an isothermal integral microreactor under the conditions of n(benzene)/n(N2O)=8-12, T=663-763 K and atmospheric pressure. Based on the reaction network proposed, the parameters in the rate model of power-law were estimated by means of Gauss-Newton optimal method with the Levenberg-Marquardt modifications, and the results were in good agreement with the experimental data.