The introduction of different reinforcement materials (yarns, fibrils, etc) into the membranes has been investigated with the aim of maintaining adequate membrane properties in terms of mechanical strength, good chemical stability, low swelling at critical temperatures and a stable electrochemical performance in PEFC. An innovative technique for the development of membranes is based on polymeric films containing polymeric nanofibres obtained through electrospinning. The electrospinning of Nafion blends with polyvinylpirrolidone (PVP) and polystyrene (PS) was investigated in this work. In particular, the morphology and diameter of electrospun fibres as a function of the electrospinning parameters and solution preparation have been studied and in both cases, a critical concentration of blend solution was found. Beaded fibres were obtained above such a concentration and, below it, only fibre mats were observed. Reinforced Nation-based membranes were realised by using the obtained spun films. Preliminary proton conductivity and fuel cell results have shown the capability of operating in a fuel cell environment with a slightly higher performance than pure Nafion but having an improved stability at high temperatures.