Nanoscaled non-woven fibers with shape memory effect are successfully fabricated via electrospinning method from Nafion solutions consisting of a little poly(ethylene oxide) (PRO). Scanning electron microscopy (SEM) investigation shows the electrospun nanofibers with average diameters in the range 170-410 nm. The electrospun nanofibers exhibit excellent shape memory properties. When deformed Nafion nanofibers are stimulated upon heat, the temporary shape responds rapidly, and then recovers to the permanent shape in less than one minute. The shape recovery ratios and shape fixity ratios of Nafion nariofibers with 0.3 wt%, 0.5 wt% and 0.7 wt% PEO are all above 90 %. In shape memory cycle, fibrous structure is stable after the stretching recovery. Shape memory Nafion nanofibers have various potential applications in smart structures and materials in the future.