Single oxygen-based advanced oxidation processes (<sup>1</sup>O<sub>2</sub>-AOPs) exhibit great prospects in selective degradation of organic pollutants. However, efficient production of <sup>1</sup>O<sub>2</sub> via tailored design of catalysts to achieve selective oxidation of contaminants remains challenging. Herein, we develop a simple strategy to regulate the components and coordination of Co-N-C catalysts at the atomic level by adjusting the Zn/Co ratio of bimetallic zeolitic imidazolate frameworks (Zn<sub><i>x</i></sub>Co<sub>1</sub>-ZIFs). Zn<sub>4</sub>Co<sub>1</sub>-C demonstrates 98% selective removal of phenol in the mixed phenol/benzoic acid (phenol/BA) solutions. Density functional theory calculations and experiments reveal that more active CoN<sub>4</sub> sites are generated in Zn<sub>4</sub>Co<sub>1</sub>-C, which are beneficial to peroxymonosulfate activation to generate <sup>1</sup>O<sub>2</sub>. Furthermore, the correlation between the origin of selectivity and well-defined catalysts is systematically investigated by the electron paramagnetic resonance test and quenching experiments. This work may provide novel insights into selective removal of target pollutants in a complicated water matrix.