The fluorination of hyperbranched polyurethane (HPU) was achieved by atom transfer radical grafting polymerization (ATRgP) of dodecafluoroheptyl methacrylate that was initiated from 2-bromoisobutyryl bromide-modified end groups of HPU. The nanofibrous membrane of fluorinated HPU was prepared by electrospinning. The structure of fluorinated HPU was characterized by Fourier-transform infrared spectroscopy (FTIR) and H-1 nuclear magnetic resonance spectrum (H-1 NMR). The surface of nanofibrous membrane was investigated with scanning electron microscope (SEM), atomic force microscope (AFM), X-ray photoelectron spectroscopy (XPS) and water contact angle (WCA) analysis, respectively. The results suggested that compared with the reported linear fluorine-containing polyurethane materials, rather high fluorine content up to 29.14% was achieved on the surface of fluorinated HPU nanofibrous membrane. Meanwhile, a superhydrophobic surface (WCA 159.7 degrees) with high adhesion to water was successfully fabricated via a convenient electrospinning process. The prepared material is promising for the application in microfluidic devices.(c) 2014 Elsevier Inc. All rights reserved.