Self-made cation exchange resin supported nanoscale zero-valent iron (R-nZVI) was used to remove phosphorus in rainwater runoff. 80% of phosphorus in rainwater runoff from grassland was removed with an initial concentration of 0.72 mg·L^–1 phosphorus when the dosage of R-nZVI is 8 g per liter rainwater, while only 26% of phosphorus was removed when using cation exchange resin without supported nanoscale zero-valent iron under the same condition. The adsorption capacity of R-nZVI increased up to 185 times of that of the cation exchange resin at a saturated equilibrium phosphorous concentration of 0.42 mg·L^–1. Various techniques were implemented to characterize the R-nZVI and explore the mechanism of its removal of phosphate. Scanning electron microscopy (SEM) indicated that new crystal had been formed on the surface of R-nZVI. The result from inductive coupled plasma (ICP) indicated that 2.1% of nZVI was loaded on the support material. The specific surface area was increased after the load of nanoscale zero-valent iron (nZVI), according to the measurement of BET-N₂ method. The result of specific surface area analysis also proved that phosphorus was removed mainly through chemical adsorption process. X-ray photoelectron spectroscopy (XPS) analysis showed that the new product obtained from chemical reaction between phosphate and iron was ferrous phosphate.