Fenton technology has excellent performance in the treatment of hard-to-degrade organics but tends to cause secondary pollution to the environment. Given its excellent adsorption capacity and the availability of mature adsorption modification studies, poly(chloromethyl styrene)-based resin (PS-Cl) has received much attention for the adsorption of heavy metal ions. However, combining the mature Fenton technology with the highly popular PS-Cl through a stable bridge to exploit the advantages of catalytic degradation performance of Fenton-like technology is the main focus of our work. The PS-NH2@FeSe2 catalyst with a core–shell structure was synthesized. The catalytic degradation of tetracycline solution in the presence of PS-NH2@FeSe2 and persulfate achieved a satisfactory effect. The removal efficiency was as high as 85.94% within 2 h, and the degradation rate constant was 0.02352 min−1. The main advantages of the PS-NH2@FeSe2 catalyst were high stability and recyclability. Thus, the catalyst would not cause secondary pollution to the environment and could still achieve a degradation efficiency of nearly 70% for TC after five times of reuse. The possible catalytic degradation pathways and potential removal mechanisms were investigated through free-radical quenching experiments and HPLC-MS detection of intermediates generated through catalytic degradation. Column experiments were conducted to investigate the effect of the catalyst on the actual removal of wastewater, and a simple flow model was developed using Yellow River water to make the integration of theory and practice possible. In conclusion, the new idea constructed with FeSe2-loaded modified resin offers promising prospects in the removal of refractory organic compounds, such as tetracycline.