Volatile Organic Compounds such as C6H6 play a crucial role in the atmosphere. In combustion processes, the reactions of hydroxyl radicals with C6H6 are important in the overall fuel oxidation system. In the current study, mechanism and rate constants of •OH radicals with benzene (C6H6 + •OH ? •C6H5 + H2O and C6H6 + •OH ? C6H5OH + H) were calculated using the CCSD(T)// B3LYP/M06-2X methods and the TST/RRKM/ME models. Calculated results reveal that •C6H5 + H2O is the main product of the reaction between benzene and •OH radicals. Also, rate constants are in good agreement with the experimental data in the moderate and high temperature range (908 – 1136 K).