A novel route toward halogen-free fire retardancy of polymers through innovative surface coating is described. Nanofiber mats based on polyimide are deposited on PA66 through electrospinning. Scanning electron microscopy is used to characterize the nanofibers. Cone calorimeter tests were performed to evaluate the fire performance. Because of their low thermal conductivity, electrospun nanofiber mats act not only as sacrificial layers but also as a protective surface that delays ignition. The effect is influenced by the fiber diameters and the imidization. Copyright (C) 2011 John Wiley & Sons, Ltd.