The poly(acrylic acid)/poly(ethylene oxide) (PAA/PEO) blend nanofibers at 100/0, 80/20, 50/50, 20/80 and 0/100 weight ratios were obtained via electrospinning process. Intermolecular interactions, miscibility and compatibility of polymer blends were studied by Fourier transform infrared (FT-IR), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and UV-visible spectrophotometer. The results suggest that intermolecular interactions have occurred between pure PAA and PEO in PAA/PEO blend. These interactions made PAA/PEO blend miscible at above-mentioned weight ratios. Additionally, the morphology and the fibers diameter were investigated using scanning electron microscope (SEM) analysis, which indicated beadless fibers with diameter range of about 120 to 300 nm. It was observed that the homogenous nanofibers with the smaller diameter were obtained in PAA/PEO blend with PAA dominant content. Finally, SEM results suggest that the formation of pure PAA nanofibers with concentration of 5.0 wt.% would not occur. Whereas, in the same concentration, pure PEO and PAA/PEO blend nanofibers with no bead defects were obtained. However, in higher pure PAA concentrations electrospun fibers were formed.