Optimized combination of novel reduced graphene oxide (rGO) wrapped anatase/rutile mixed phase TiO2 nanofibers (MPTNFs) synthesized by an efficient route of electrospinning together with the help of easy chemical methods has reported to enhance the photocatalytic performance. The mesoporous MPTNFs/rGO composites were characterized by X-ray diffraction, Raman spectroscopy, scanning electron microscopy, and transmission electron microscopy. The photocatalytic activity was evaluated by degradation of methyl orange. A significant increase in the reaction rate was observed with TiO2/rGO materials under UV light irradiation. The synergistic effect of anatase/rutile mixed phase in one dimensional nanostructure and the electronic interaction between TiO2 and rGO provided the subsequent improvement of electron transfer. These intriguing peculiarities also reduced the charge recombination for enhancement of catalytic efficiency. © 2016 Elsevier Ltd.