Carbon-layer-coated TiO2/WO3 nanofibers (WTC) were fabricated by combining the electrospinning technique (for TiO2/WO3 nanofibers) and hydrothermal method (for carbon shell). The structure characterization results showed that TiO2/WO3 nanofibers (WT) were encased within an uniform carbon shell about 10 nm in thickness. By adjusting the content of WO3, the graphitization degree of carbon layer could be controlled, and the WTC nanofibers had remarkable light absorption in the visible region. Furthermore, the photoelectrochemical performance and photocatalytic activity were investigated systematically. As expected, the H-2-generation rate of the as-prepared composite materials was greatly enhanced compared with pure TiO2 nanofibers (TNFs), TiO2/WO3 nanofibers (WT) and TiO2@carbon core/shell nanofibers (TC). The enhanced activities were mainly attributed to the multichannel-improved charge-carrier photosynthetic heterojunction system with the carbon layer on the surface of TiO2 as an electron collector and WO3 as a hole collector, leading to effective charge separation on these components, which were evidenced by photoluminescence spectroscopy (PL), electrochemical impedance spectroscopy (EIS) and photocurrent analysis. Besides, the addition of WO3 promoted the graphitization of carbon layer, which in turn improved transport of electrons in the carbon layer and also contributed to the performance improvement. (C) 2016 Elsevier B.V. All rights reserved.