Hydrogen bonded Poly(acrylic acid)-poly(ethylene oxide) interpolymer nanofibrous membranes containing the well-arranged/dispersed exfoliated Na-montmorillonite platelets obtained successfully by the electrospinning technique. The as-spun composite nanostructures were characterized by X-ray diffraction patterns and electron microscopy, confirm the formation of a favoring ordered exfoliated architecture along the fiber axis. Thermal analysis suggested that increase in both the thermal stability and the melting point of the as-synthesized composite nanostructures could be a result of ordered exfoliated morphology as well as the well-distributed clay platelets along the fiber axis. Improved morphological and thermal properties assigned to aligned clay platelets induced by the electrospinning technique make the as-spun non-woven membranes more promising candidates in tissue engineering, drug delivery, fuel cell proton exchange membranes and environmental pollution treatment applications.