The effect of phosphate on adsorption and oxidation of catechol, 1,2-dihydroxybenzene, in a heterogeneous Fenton system was investigated. In situ attenuated total reflectance infrared spectroscopy (ATR-FTIR) was used to monitor the surface speciation at the nano-Fe 3 O 4 catalyst surface. The presence of phosphate decreased the removal rate of catechol and the abatement of dissolved organic compounds, as well as the decomposition of H 2 O 2 . This effect of phosphate was mainly due to its strong reaction with surface sites on the iron oxide catalyst. At neutral and acid pH, phosphate could displace the adsorbed catechol from the surface of catalyst and also could compete for surface sites with H 2 O 2 . In situ IR spectra indicated the formation of iron phosphate precipitation at the catalyst surface. The iron phosphate surface species may affect the amount of iron atoms taking part in the catalytic decomposition of H 2 O 2 and formation of hydroxyl radicals, and inhibit the catalytic ability of Fe 3 O 4 catalyst. Therefore, phosphate ions worked as stabilizer and inhibitor in a heterogeneous Fenton reaction at the same time, in effect leading to an increase in oxidation efficiency in this study. However, before use of phosphate as pH buffer or H 2 O 2 stabilizer in a heterogeneous Fenton system, the possible inhibitory effect of phosphate on the actual removal of organic pollutants should be fully considered.