Electrospinning process produces fibers in the range of submicron to nanometer scale and this novel technique has opened up new and improved application of electrospun nanofibers. Our research is focused on applying these nanofibers in the area of national defense and value added products such as decontamination wipes, chemical protective clothing, highly efficient filters, etc. Polyurethane and polyethylene oxide nanofibers in the range of 50 to 300 nm have shown high potentials for their applications in these top priority research areas. The first known selfassembling phenomenon in polyurethane nanofibers has been observed and these self-assembled nanofibers will be of enormous value in chemical countermeasures substrates such as facemasks and chemical protective clothing liners. On the other hand, metal oxide embedded polyethylene oxide nanofibers can serve as a self-detoxifying substrate due to its reactivity against chemical warfare agents, organophosphorous pesticides and industrial toxic chemicals.