Highly ordered TiO2 nanotube arrays prepared by anodic oxidation have attracted increasing research interests due to their promising applications in many scientific areas. To the best of our knowledge, a factor limiting the application of TiO2 nanotube arrays was their long sustaining reaction time by anodic oxidation, usually lasting 6–12 h and even longer when synthesizing thicker nanotubular layers. In the present paper, we reported for the first time a facile but effective approach to accelerate the anodic formation of TiO2 nanotube arrays by proper addition of sodium carbonate (Na2CO3) into the anodization electrolyte. We adopted the 0.3M NH4F + 0.03M Na2CO3 + EG (ethylene glycol) + 3.0 vol.% H2O electrolyte and the average growth rate of the nanotubes achieved in our experiments could be accelerated to 1100 nm/min. The possible mechanism of the rapid electrochemical process was also presented.