2.5GHz of microwave irradiation can cause a considerable improvement of oxidative decomposition of aqueous phenol in a UV/H2O2 system. The experimental results showed that the microwave irradiation can raise both the phenol conversion and the TOC removal efficiency up to or above 50%. Also, the microwave irradiation could considerably enhance the oxidative degradation of phenol in the UV/H2O2 system even under a suppression of thermal effect. Addition of hydrogen peroxide by more than a stoichiometric amount was critical to mineralize aqueous phenol to create a short reaction time. Also, microwave irradiation can accelerate the degradation rate of intermediates, hydroquinone and catechol, produced in the course of phenol oxidative decomposition. From the kinetic study, the disappearance rate of phenol can be expressed as dX/dt = kPH[M]0(alpha - X)(1 - X), where alpha equivalent [H2O2]0/[M]0 + kOH[OH*]/kPH[M]0, shows a good correlation with the experimental data. The kinetic analysis showed that an indirect reaction of phenol with OH radical might be dominant in the absence of microwave irradiation, meanwhile a direct reaction of phenol with hydrogen peroxide might be dominant in the presence of microwave irradiation except for low concentrations of hydrogen peroxide.