Electrospinning of blend systems, combining two or more polymers, has gained increasing interest for the fabrication of fibers that combine properties of the individual polymers. Here, a versatile method to produce hydrophobic fibers composed of poly(vinylidene fluoride-co-hexafluoropropylene) (PVDFhfp) and polyurethane (PUR) is presented. PVDFhfp containing fibers are expected to reduce protein adsorption. In a one-step process, blend solutions are electrospun into homogeneous nonwoven membranes with fiber diameters in the range of 0.6 +/- 0.2 to 1.4 +/- 0.7 mu m. Surface fluorine concentrations measured by X-ray photospectroscopy show an asymptotic dependency in function of the PVDFhfp to PUR ratio, reaching values close to pure PVDFhfp at a weight per weight ratio of 10% PVDFhfp to 90% PUR. This fluorine enrichment on the surface suggests a gradient structure along the fiber cross-section. At increased surface fluorine concentration, the contact angle changes from 121 +/- 3 degrees (PUR) to 141 +/- 4 degrees (PUR/PVDFhfp). Furthermore, these highly hydrophobic fibers present significantly reduced fibrinogen or albumin adsorption compared to PUR membranes.