Carbon and potassium-embedded TiO2 nanotube arrays were rapidly formed via anodic oxidation of the Ti metal in ethylene glycol (EG) containing potassium hydroxide (KOH). The incorporation of KOH allowed the simultaneous control of electrochemical oxidation and chemical dissolution, resulting in the equilibrium growth of nanotube arrays with a maximum growth rate of similar to 353 nm min(-1). The anodic growth of nanotube arrays in the hydroxyl (OH)-rich environment induced the formation of anatase crystallites by bridging between the dissociated H2O molecules and OH group of octahedra in TiO2. High aspect ratio nanotube arrays with a large pore size formed in EG electrolyte containing KOH could efficiently harvest the light energy, thereby enhancing the photocatalytic efficiency. High reaction sites of nanotube arrays with high surface area promoted the diffusion of charge carriers to the electrolyte. Furthermore, the strong e(-) donation nature of adsorbed-potassium species on nanotubes facilitated the photoelectrochemical properties. Nanotube arrays formed in EG electrolyte containing 1 wt% of 1.0 M KOH exhibited a remarkable capability to generate hydrogen at an evolution rate up to similar to 658.3 mu l min(-1) cm(-2) and the photoconversion efficiency of similar to 2.5%. (C) 2012 Elsevier Ltd. All rights reserved.