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Chloride ion significantly impacts the degradation efficiency of organic pollutants in chemical industrial wastewater during electrocatalytic process, therefore utilization of Cl−to in situ produce reactive chlorine species (RCS) is desired for electrocatalytic degradation of pollutants. We developed a novel catalyst by incorporating Zn into CoOx(ZnnCoOx) as anode for the electrocatalytic removal of 4-chlorophenols (4-cp) in Cl−-containing wastewater. Characterization and electrochemical performance of ZnnCoOxcatalysts indicated that Zn incorporation increased Co2+/Co3+ratio, resulting in lattice distortion and the formation of oxygen vacancy (OV). Electrocatalytic experiments showed that Zn2CoOx(i.e., ZnCo = 2:1) had the highest electrochemical reactivity, and the 4-cp degradation rates (kobs) showed a positive correlation with OV. The identified reactive species involved in 4-cp degradation included O2•−and RCS. The formation mechanism of reactive species and the degradation pathways of 4-cp during electrocatalytic process using the Zn2CoOxanode were proposed. Overall, the developed ZnnCoOxcatalyst as anode can utilize Cl−to in situ produce RCS and exhibit an effective performance on the 4-cp degradation in Cl−-containing wastewater.