Different concentrations of electrospun nanofibers of poly(vinylidene fluoride) (PVDF)/polyacrylonitrile (PAN) blends were prepared. The surface morphology of the nanofibers was studied by optical microscopy and scanning electron microscopy (SEM). Atomic force microscopy (AFM) was used to study the surface roughness. The change in the functional groups of PVDF after blending with PAN was investigated by Fourier transform infrared (FTIR). The wettability was examined to characterize the surface morphology of the blends. The effect of PAN content on the blend fiber was also studied for UV-vis absorption spectra before and after exposure to UV radiation.