Cr(VI) and phenol are toxic contaminants that need to be treated, and different methods have been researched to simultaneously remove these two contaminants from industrial wastewater. In this study, Cr(VI) was used as a novel Fenton-like catalyst in phenol degradation by H₂O₂. In the pH range of 3.0‒11.0, the degradation efficiency of phenol decreased with elevated pH. At pH = 3.0, 100 mg/L phenol was effectively degraded by 2 mmol/L Cr(VI) and 20 mmol/L H₂O₂. At pH = 7.0 and the same conditions as those of pH = 3.0, 79% of 100 mg/L phenol was removed within 6 h, which was an improvement in pH limitation compared with the Fe(II)-mediated Fenton reaction. Quenching experiments indicated that ^·OH generated from the catalysis of H₂O₂ by Cr(V) instead of Cr(VI) was the primary oxidant that degraded phenol. When pyrophosphate was added in the Cr(VI)/H₂O₂ system, complexes with the Cr(V) intermediate rapidly formed and inhibited H₂O₂ decomposition, implying that the decomposition of H₂O₂ to ^·OH was catalyzed by Cr(V) instead of Cr(VI). The presence of anions such as chloride and sulfate had insignificant effect on the degradation of phenol. TOC and UV analyses suggest that phenol could not be completely oxidized to CO₂ and H₂O, and the intermediates identified by high performance liquid chromatography further indicates that maleic acid and benzoquinone were intermediates which may be further degraded into short chain acids, primarily maleic, formic, acetic, and oxalic acids, and eventually into CO₂ and H₂O. Considering that more than 50% Cr(VI) can also be removed during this process, the Cr(VI)/H₂O₂ system is more appropriate for the simultaneous removal of Cr(VI) and phenol contaminants from industrial wastewater.