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In this study, we investigate Mn-doped CeO2nanoribbons as photocatalysts to address the issue of performance enhancement in volatile organic compounds (VOCs) removal. Our primary focus centers on elucidating the interplay between charge rearrangement and local electric field (LEF) effects to uncover how these key factors collectively contribute to the improved photocatalytic performance. The successful doping of Mn atoms into the CeO2lattice resulted in a strong dopant/matrix interaction effect. In situ XPS and density functional theory (DFT) calculations confirmed significant local charge rearrangement due to the dopant-induced local electric field, promoting charge carrier separation. The Mn dopant facilitated the generation of superoxide and hydroxide radicals. DFT simulations showed that Mn doping promoted VOCs adsorption on CeO2, favoring the subsequent oxidation process. The Mn-doped CeO2nanoribbons achieved enhanced photodegradation performance of HCHO and CH3COCH3compared to CeO2. This work aims to provide guidance and insights for the development of advanced photocatalysts.