Zinc oxide (ZnO) nanoparticles, self-assembled in the form of one dimensional ZnO nanofibers were synthesized using electrospinning technique from solution of polyvinyl alcohol (PVA) and zinc acetate followed by calcination at 600°C in oxidizing environment. Scanning Electron Microscope (SEM) analysis demonstrates that morphology of ZnO nanofibers having rough surface and corresponding Energy Dispersive Spectrometry (EDAX) confirmed the Zn: O atomic ratio approximately in 50:50. Transmission electron microscopy (TEM) images clearly demonstrate the rough morphology is due to the self-assembling of ZnO nanoparticles having diameter approximately 50nm. X-ray Diffraction (XRD) reveals the polycrystalline structure and Raman spectra show some shifts in phonon modes. The PL graph show exceptional emission at 342nm due to band-band transition. Under solar radiations as produced ZnO nanofibers degrades the 99% of 25ppm acid fuchsine which proven through UV spectra when compared to blank dye solution. This shows that natural solar radiations are sufficient to excite theses self-assembled high surface area ZnO nanofibers to show its photocatalytic activity.