Abstract Herein, a novel sunlight‐independent tribocatalytic system with efficient friction energy harvesting capability is proposed. This system demonstrates enhanced tribocatalytic performance of cerium oxide (CeO 2 ) nanoparticles driven by the friction between Cu coated on the glass beaker bottom and a Teflon (PTFE) magnetic disk. An apparent rate constant of 0.045 min −1 was achieved for methylene blue (MB) degradation, representing a 2.7‐fold improvement over the CeO 2 @glass/PTFE system (0.01682 min −1 ). Notably, the system achieved > 90% degradation efficiency for high‐concentration MB solutions (40 mg/L), surpassing the performance of previously reported tribocatalytic systems. Through multiscale tribo‐interface characterization and radical trapping experiments, the synergistic catalytic mechanism was elucidated: Friction‐induced charge carriers in CeO 2 are efficiently transferred via the interfacial electronic effects of the Cu/PTFE friction couple and the active surface with Ce 3+ /Ce 4+ redox couples. Electron paramagnetic resonance analysis confirmed that Cu coating modification on the surface of the beaker bottom enhanced hydroxyl radical (·OH) yield by 2.3‐fold compared to glass, enabling complete pollutant degradation through hole (h + )‐dominated oxidation pathways. This work transcends conventional catalyst modification strategies, establishing a new paradigm for interface engineering in mechano‐chemical energy conversion systems.