The irrational application of herbicides has led to severe water contamination by atrazine and other pesticides. To solve this issue, a mixed-linker metal-organic framework (MOF) photo-Fenton catalyst, Fe-PCN-134, was prepared and evaluated for atrazine degradation in water. Fe-PCN-134 could degrade atrazine up to 99.41% in ~80 min and could be used stably for four cycles. Atrazine degradation conformed to pseudo-first-order kinetics, with a rate constant ~103 times that of Fe(III)tetrakis(4-carboxyphenyl)porphyrin chloride. In the mixed junction MOF, the introduction of tetrakis(4-carboxyphenyl)porphyrin and Fe3+ coordination could reduce the material bandgap, improving the separation and transport efficiencies of photogenerated electron-hole pairs. Further, the material could undergo a Fenton reaction during the photocatalytic reaction, ultimately producing h+, ·OH, ·O2− and 1O2 and thereby accelerating atrazine degradation. The safety and feasibility of using Fe-PCN-134 in pesticide-contaminated water treatment have been demonstrated by testing the plant and cell toxicity of the water after the photo-Fenton treatment.