We report an efficient, highly selective, and low temperature graphene-catalyzed reaction process for one-step oxidation of benzene to phenol with hydrogen peroxide as the oxidant. The chemically converted graphene (CCG) from small graphite was used as the catalyst. The conversion of benzene reaches 18%, with phenol being the sole product. The catalyst was reusable and very stable. By XPS, C K-edge X-ray absorption spectra, benzene-TPD, and kinetic measurements, it was concluded that the moderate H₂O₂ activation rate, good benzene adsorption ability, and balanced kinetic control over the oxidation reaction are responsible for the outstanding catalytic performance of the metal-free catalyst.