A high-performance, durable, low-cost, and environmentally friendly catalyst is highly desired in advanced oxidation processes (AOPs) for water treatment. Considering the activity of Mn(Ⅲ) and the superior catalytic properties of reduced graphene oxide (rGO) in peroxymonosulfate (PMS) activation, rGO-modified MnOOH nanowires (MnOOH-rGO) were fabricated by a hydrothermal method for phenol degradation. The results showed that the composite synthesized at 120 °C with 1 wt% rGO dopant exhibited the best performance for phenol degradation. Nearly 100% of the phenol was removed by MnOOH-rGO within 30 min, which is higher than the removal rate of pure MnOOH (70%). The effects of catalyst dosages, PMS concentration, pH, temperature, and anions (Cl⁻, NO₃⁻, HPO₄²⁻and HCO₃⁻) on phenol degradation were investigated. The removal rate of chemical oxygen demand (COD) reached 26.4%, with a low molar ratio of PMS to phenol at 5:1 and a high PMS utilization efficiency (PUE) of 88.8%. The phenol removal rate remained more than 90% after five recycle with less than 0.1 mg L⁻¹ leakage of manganese ions. Together with the results of radical quenching experiments, X-ray photoelectron spectroscopy (XPS) and electron paramagnetic resonance spectroscopy (EPR), electron transfer and ¹O₂ were proved to dominate the activation process. During the direct electrons transfer process, the electrons transfer from the phenol to PMS by using the Mn(Ⅲ) as the mediate with a stoichiometric ratio between PMS and phenol at 1:2, which mainly contributed to the high PUE. This work provides new insight into a high-performance Mn(Ⅲ) based catalyst on PMS activation with high PUE, good reusability, and environmentally friendly for removing organic pollutants.