Highly ordered boron-doped TiO2 nanotube arrays were fabricated via a facile electrodeposition method. X-ray photoelectron spectroscopy (XPS) analysis revealed incorporated B atoms in the lattice of a TiO2 nanotube array. The X-ray diffraction (XRD) spectrum indicated improved crystallinity of boron-doped TiO2 nanotube arrays, relative to undoped TiO2 nanotube arrays. A shift of the absorption edge toward the Visible region and a new absorption shoulder (380-510 nm) of boron-doped TiO2 nanotube arrays were observed via diffuse reflectance spectroscopy (DRS). In photoelectrochemical measurements, under either ultraviolet (UV) or visible-light irradiation, the photocurrent conversion efficiency was enhanced because of boron doping. The photoelectrocatalysis of phenol under simulated solar irradiation was performed using boron-doped or undoped TiO2 nanotube arrays, and the kinetic constant of a boron-doped TiO2 nanotube array photoelectrode was increased by ca. 28% compared to that of an undoped TiO2 nanotube array photoelectrode.