In this work, taking FeWO4 nanosheets as an example, the activation of oxalic acid (OA) based on facet engineering for the enhanced generation of active radical species was reported, revealing unprecedented surface Fenton activity for pollutant degradation. Density functional theory calculations confirmed the more efficient generation of reactive oxygen species over FeWO4 nanosheets with the {001} facet exposed (FWO-001) under visible light irradiation compared to the efficiency of FeWO4 nanosheets with the {010} facet exposed (FWO-010), which could be attributed to a higher density of iron and the efficient activation of OA on the {001} facet. The H2O2-derived •OH tended to diffuse away from the active sites of FWO-001 into solution to favor the continuous activation of OA into the active radicals for pollutant redox reactions, but preferred to remain on FWO-010 to hinder the further activation of OA on the {010} facet. Additionally, the generation of •CO2- endowed FeWO4 with a strong reduction ability. Compared with FWO-010, FWO-001 exhibited enhanced redox activity for the catalytic degradation of organic pollutants and Cr(VI) in the optimized conditions. These findings can help in understanding the facet dependent surface Fenton chemistry of catalytic redox reactions and in designing efficient catalysts for environmental decontamination.