Ti-Fe alloys with Fe contents of 0.05, 0.5 and 1.0 wt% were obtained using the arc-melting method. Fe-doped TiO2 nanotube arrays were prepared by anodizing Ti-Fe alloys in ethylene glycol solution containing 0.25 wt% NH4F and 10 wt% H2O. The microstructure, crystal structure and photoelectrochemical properties of the nanotube arrays were characterized using scanning electron microscopy, X-ray diffraction, UV-Vis diffuse reflectance spectroscopy and electrochemical analyzer. Results show that doping of 0.05 wt% Fe improves the photoelectrochemical properties of titania nanotube arrays significantly, whilst further increasing the Fe contents to 0.5 and 1.0 wt% degrades these properties. The external potential has a considerable influence on the photocurrent density at doping content of 0.5 wt% Fe.