Alginate–Fe 2+ /Fe 3+ polymer coated Fe 3 O 4 magnetic nanoparticles (Fe 3 O 4 @ALG/Fe MNPs) with core/shell structure are prepared and used as heterogeneous Fenton nanocatalyst to degrade norfloxacin (NOF). The Fenton-like process based on Fe 3 O 4 @ALG/Fe shows much higher efficiency on NOF degradation. Compared with Fe 3 O 4 nanoparticle–H 2 O 2 system, NOF degradation in Fe 3 O 4 @AlG/Fe–H 2 O 2 system can be conducted in a wide pH range (pH 3.5–6.5) and independent on temperature. With 0.98mM H 2 O 2 and 0.4gL −1 Fe 3 O 4 @ALG/Fe, 100% of NOF and 90% of TOC is removed within 60min, and the fluorine element in NOF molecule changes into F − ions within 1min, indicating that NOF degradation in this Fenton-like reaction is performed through direct defluorination pathway. XPS analysis shows that TOC removal in reaction solution mainly results from the adsorption of NOF degradation intermediates on catalyst. Due to the paramagneticity and high saturation magnetization of Fe 3 O 4 @ALG/Fe, the used catalyst with adsorbed NOF intermediate is collected from aqueous solution by applying an external magnetic field, leading to complete removal of NOF from water samples. As being composed of inorganic materials and biopolymer, Fe 3 O 4 @ALG/Fe MNPs are robust, thermo-stable, nontoxic and environmentally friendly. These attractive features endow Fe 3 O 4 @ALG/Fe as a potent Fenton-like catalyst for fluoroquinolones degradation.