Conventional methods are inefficient to treat water contaminated with persistent organic contaminants. To decontaminate bacteria and 2,4,5‐trichlorophenol (TCP) contaminated water, a heterogeneous photocatalysis‐based advanced oxidation process was applied in this study. A Li‐doped ternary Zn0.5Ni0.5Fe2O4 (ZNF) photocatalyst (Li/ZNF) was synthesized via a facile co‐precipitation technique and characterized. The Li/ZNF has a sufficient specific surface area (69.8 m2.g−1), and an appropriate bandgap of 2.89 eV. Under optimal conditions, 10 mg of Li/ZNF photocatalyst degraded 80 % of 50 mg L−1 TCP in 6 h at pH 3 in the presence of 4 mM H2O2. After use, the Li/ZNF photocatalyst was magnetically separated and reused numerous times, with an efficiency of 66 % after the fifth reuse cycle. In the antibacterial time‐kill assay, 15 and 25 mg of Li/ZNF inhibited 1×107 CFU.mL−1 of S. Aureus and E. coli bacteria after 60 min of UV exposure, respectively.