The peroxymonosulfate (PMS)-triggered radical and nonradical active species can synergistically guarantee selectively removing micropollutants in complex wastewater; however, realizing this on heterogeneous metal-based catalysts with single active sites remains challenging due to insufficient electron cycle. Herein, we design asymmetric Co–O–Bi triple-atom sites in Co-doped Bi₂O₂CO₃ to facilitate PMS oxidation and reduction simultaneously by enhancing the electron transfer between the active sites. We propose that the asymmetric Co–O–Bi sites result in an electron density increase in the Bi sites and decrease in the Co sites, thereby PMS undergoes a reduction reaction to generate SO₄^•- and •OH at the Bi site and an oxidation reaction to generate ¹O₂ at the Co site. We suggest that the synergistic effect of SO₄^•-, •OH, and ¹O₂ enables efficient removal and mineralization of micropollutants without interference from organic and inorganic compounds under the environmental background. As a result, the Co-doped Bi₂O₂CO₃ achieves almost 99.3% sulfamethoxazole degradation in 3 min with a k-value as high as 82.95 min⁻¹ M⁻¹, which is superior to the existing catalysts reported so far. This work provides a structural regulation of the active sites approach to control the catalytic function, which will guide the rational design of Fenton-like catalysts.