Novel fluorinated cross-linked polyphosphazene micro-nano spheres have been prepared by precipitation polymerization of hexachlorocyclotriphosphazene (HCCP) monomer. The influence of molecular structure on the morphology of polyphosphazene micro-nano spheres was investigated by SEM and TEM. The micro-nano spheres were also characterized by Fourier transforms infrared, X-ray photoelectron spectroscopy and thermo gravimetric analysis. The results indicate that the 5 % thermal degradation temperature is 366 A degrees C. It was found that a silicon wafer dip-coated with thus prepared micro-nano spheres has a water contact angle as high as 137A degrees A A +/- A 1.5A degrees. Furthermore, the effects of the concentration of HCCP and ultrasonic power on the morphology were also discussed.