In the present study, one dimensional nickel oxide (NiO) nanofibers were successfully fabricated using an inexpensive and simplistic electrospinning technique to evaluate their efficient applicability as a photocatalyst in dye degradation processes. The synthesis part involves the calcination of electrospun poly(ethylene oxide)/nickel acetate tetrahydrate nanofibers to obtain phase pure cubic NiO nanofibers, which were further characterized using various techniques to determine their physical and chemical properties. Furthermore, the photocatalytic activity of these NiO nanofibers along with their kinetics of degradation was studied with the photodegradation of model dye Congo red (CR) under visible light irradiation. Interestingly, the photocatalytic properties of the NiO nanofibers were found to be better than those of the nanoparticles when compared, and were found to be dependent on the concentrations of the loaded photocatalyst. Besides this, the stability of the nanofibers in aqueous solution was examined along with their reusability.