We proposed a feasible strategy to prepare a rigid-flexible coupled polyphosphazene supported polyurethane foam (PUF-PCP) adsorbent by in situ polycondensation between hexachlorocyclotriphosphazene and polyethyleneimine on the surface of polyurethane foam (PUF) at room temperature. Owing to combination of the open cell porous structure of PUF support and the superior adsorption capacity of PCP coatings, the PUF-PCP composite adsorbent exhibited good adsorption behavior towards anionic dyes. Especially, the experimental adsorption capacity of PUF-PCP for methyl orange (MO) dye was up to 978.56 mg g−1 at 25 ºC. The relative separation factors of MO for methylene blue, crystal violet and rhodamine B were 224.1, 78.1 and 161.8 respectively, exhibiting an excellent adsorption selectivity of PUF-PCP towards MO. Moreover, the used PUF-PCP adsorbent can be easily collected and regenerated. The adsorption test data were best explained by Langmuir model and pseudo-second-order model. The adsorption process of MO onto PUF-PCP was spontaneous and endothermic. XPS and FT-IR analysis confirmed that electrostatic adsorption and hydrogen bonding were the plausible uptake mechanism of PUF-PCP for MO molecules. The present work demonstrated that PUF-PCP has promising potential in removing environmental anionic pollutants from waterbody.