Combining mechanical properties with enhanced cell interaction is highly desirable in a biomaterial. In this study, a new paradigm for enhancing the mechanical properties of segmented polyurethanes (SPUs) through solution blending with a biopolymer is presented. This noncovalent approach is based on the premise that molecular level blending of SPUs rich in hydrogen bonding (H bonding) domains with a biopolymer capable of H bonding will promote H-bond bridges between the components, leading to molecular annealing and modification of the physicochemical properties of the SPU. We demonstrate that by solution-blending solubilized elastin with a triblock copolymer-derived SPU, a 5-fold increase in tensile modulus of electrospun constructs of the SPU can be achieved, with concomitant enhancement in human endothelial cell attachment. Spectroscopic and calorimetric analysis confirm the role of H bonding in the enhancement, thus providing the impetus to further explore blending with biopolymers as a means of improving the property profiles of synthetic polymeric biomaterials.