Cetyltrimethylammonium bromide (CTAB) modified bentonite supported KMnO4 (KMnO4/CTAB-bent) was prepared by solid-phase grinding method, and applied to phenol removal from wastewater. Factors affecting efficiency, such as activated temperature, initial solution pH, KMnO4/CTAB-bent dosage, phenol initial concentration and reaction temperature on degradation were investigated. It was found that pH significantly affected the degradation and chemical oxygen demand (COD) removal efficiency. The results show that over 92% degradation and 60.58% COD removal efficiency can be obtained in 30 min. The surface properties and structure of KMnO4/CTAB-bent were measured by X-ray diffraction, X-ray photoelectron spectroscopy, Brunauer–Emmett–Teller, and Fourier transform infrared spectroscopy. However, it was demonstrated that the KMnO4/CTAB-bent was deactivated quickly during phenol degradation after the second cycle, indicating that the stability of KMnO4/CTAB-bent needs to be further improved.