In the present work, we reported the fabrication of Fe-doped WO3 nanofibers via a versatile electrospinning method towards efficient photoelectrochemical (PEC) water splitting. The resultant Fe-WO3 nanofibers had a high purity in morphology, and the Fe doping levels within the WO3 nanofibers were controlled in the range from 0.32 to 1.47 at.%, making the band gaps of WO3 nanofibers tailored from 2.92 to 2.8 eV. The incorporated Fe dopants could not only increase the light absorption, but also improve the charge transport and charge transfer efficiencies, bringing an enhanced PEC activity of the WO3 nanofiber photoanodes. The WO3 nanofibers with the optimized 0.32 at.% Fe doping level exhibit the best PEC performance. The mechanism for the enhanced PEC behaviors was proposed.