Novel fluorinated cross-linked polyphosphazene microspheres bearing active amino groups on the surface have been successfully prepared by precipitation polymerization of hexachlorocyclotriphosphazene (HCCP) with 2,2'-bis(trifluoromethyl)-4,41-diaminodiphenyl ether (6FODA) through different strategies: ultrasonic in high temperature and water-triggered self-assembly in normal temperature. By adjusting the reaction conditions, the diameter of the microspheres were controlled from 0.5-3 mu m and 0.2-1 mu m respectively. The chemical structures, morphologies, thermal properties, and surface properties of these microspheres were investigated by Fourier transform infrared (FTIR), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), differential scanning calorimetry (DSC), thermogravimetric analyzer (TGA), and water contact angles (WCA). The cross-linked structures exhibited remarkable thermal stability, and no glass transition temperatures were observed. It was found that a wafer coated with those prepared microspheres has a water contact angle around 135 degrees, which definitely increased compared with the water contact angle of as-prepared poly(hexachlorocyclotriphosphazene-co-4,4'-diaminodiphenyl ether) microspheres (about 8.8 degrees). (C) 2017 Elsevier B.V. All rights reserved.