The star-shape anionic/non-ionic polyurethane-acrylate (SPUA) was prepared via “arm-first” technique, the effects of the content of non-ionic extender (PEG 600) on the properties of emulsion and film after UV curing were researched, and the structure of SPUA was confirmed by FT-IR. Results show that: The content of PEG 600 change obviously particle size distribution, surface tension and rheology behavior of emulsion. Micro-phase separation of SPUA is not obvious, and compatibility between soft segment and hard segment is good. With increasing content of PEG 600, ultimate strength, solvent-resistance of film after UV curing, glass transition temperature(Tg) of soft segment raise, which elongation at break, tensile-recovery ratio, water-resistance, thermal stability of film after UV curing decline.