In this study, we utilized the carbon precursor derived from walnut shells to synthesize a series of Ce‐modified Cu‐based carbon catalysts (Cu−Ce/AC) via the impregnation method. We investigated the performance and stability of Cu−Ce/AC catalysts for CWAO phenol after H2 reduction at various temperatures. The Cu−Ce/AC‐250 catalyst exhibited its highest performance at 250 °C, achieving complete phenol conversion. Characterization results from techniques including XRD, BET, FTIR, ICP‐OES, SEM‐EDS, XPS, and H2‐TPR indicated that the active components of the H2‐reduced catalysts were more evenly distributed across the catalyst surface, thereby enhancing the availability of reactive sites for phenol oxidation. Simultaneously, under the appropriate temperature, the H2 atmosphere can reduce a portion of the Cu2+ on the catalyst surface to Cu+, thereby mitigating the loss of Cu components.