Poly(cyclotriphosphazene-co-4,4′-diaminodiphenyl ether) microspheres (PZA) was based on hexachlorocyclotriphosphazene (HCCP) and 4,4′-diaminodiphenyl ether (ODA). It was synthesized via one-step precipitation method. The PZA microspheres were characterized by FT-IR, XPS, zeta potential and SEM/EDS. Through experimental research, PZA microspheres had the optimal adsorption performance with pH value 3.5, contact time of 60min, thorium(IV) ions concentration of 30mgL−1, and PZA microspheres of 10mg. The maximum adsorption capacity of PZA micros...