The dispersing effect of carbon materials on nanoparticles can enhance the full exposure of their active sites. Herein, phosphorus (P)-doped activated carbon-supported trace cobalt ferrite composites (P-CoFe@BCX) were achieved by two-step pyrolysis for efficient peroxymonosulfate (PMS) activation and water pollution remediation. The removal efficiency of 2,4-dichlorophenoxyacetic acid (2,4-D) was optimized by adjusting the coupling ratio of carbon substrate and cobalt ferrite. P-CoFe@BC5/PMS oxidation system (0.10 g L-1, 0.50 mM) eliminated 98.3% of 2,4-D (20.0 mg L-1) within 60 min at unadjusted pH. The constructed adsorption enrichment and oxidative degradation pathways are highly efficient in utilizing reactive oxygen species (ROS), and the dual tracks of free and non-free radicals achieve the rapid degradation of 2,4-D. P-doped activated carbon acts as an electron shuttle to accelerate electron transfer between active sites and enhances the adsorption efficiency of 2,4-D and PMS onto the composites. In addition, the P-CoFe@BC5/PMS oxidation system still exhibited strong 2,4-D removal performance at a wide pH range of 2.0–10.0. The inhibitory effect of environmental components was related to their concentration, such as chloride, bicarbonate, sulfate and humic acid. Density functional theory calculations show that ROS tends to attack the CO bond on the 2,4-D branch chain, and the degradation products show lower biological toxicity. Hence, the constructed cobalt ferrite anchored P-doped activated carbon activated PMS system has great potential in treating organic wastewater.