Photocatalysis has been proved a promising technology to alleviate the deterioration of environments by utilizing light energy. High efficiency and cycling stability are important for pollutant degradation in practical wastewater treatment. Herein we prepared C/titania@reduced graphene oxide nanofibers (C/TiO2@RGO NFs) by electrospun polyacrylonitrile/titania nanofibers (PAN/TiO2 NFs) wrapped with graphene oxide (GO)assisted with polydopamine, followed by one-step GO reduction, TiO2 crystallization and interface enhancing between anatase TiO2 and graphene by forming chemical bonding via heat treatment. The as-prepared C/TiO2@RGO NFs exhibited four times photocatalytic efficiency higher than commercial catalyst P25, and they also exhibited favorable cycling stability for methylene blue degradation under visiblelight illumination. The high photocatalytic efficiency is mainly attributed to the efficient charge separation and broadening visible light absorption originating from the interface enhancing between TiO2 and RGO. This work provides an insight to design more efficient graphene-based semiconductor photocatalysts for pollutant decomposition.