Abstract: Highly ordered arrays of TiO2 nanotubes (TiNTs) were grown vertically on Ti foil by electrochemical anodization. We controlled the lengths of these TiNTs from 2.4 to 26.8 ¶üÇóμm while varying the water contents (1, 3, and 6 wt%) of the electrolyte in ethylene glycol in the presence of 0.5 wt% NH4F with anodization for various applied voltages (20–80 V), periods (10–240 min) and temperatures (10–30 oC). For vertically aligned TiNT arrays, not only the increase in their tube lengths, but also their geometric (wall thickness and surface roughness) and crystalline structure lead to a significant influence on photocatalytic activity. The length optimization for methylene blue (MB) photodegradation was 18 μm. Further extending the TiNT length yielded lower photocatalytic activity presumably related to the limited MB diffusion and light-penetration depth into the TiNT arrays. The results indicated that a maximum MB photodegradation rate was obtained for the discrete anatase TiO2 nanotubes with thick and rough walls.