Titanium dioxide nanotube arrays (TNTAs) were fabricated by electrochemical anodization of Ti foils. The effects of electrolyte, applied voltage, duration of anodic oxidation to morphology, and photocatalytic performance of TNTAs were investigated. TNTAs formed in electrolyte of glycol and DMSO tend to grow along radial direction with flimsy tube wall and weak adhesion on Ti substrate. Those in glycerol, however, easily achieve balance between growth rate and corrosion rate, form orderly arranged array of nanotubes with uniform diameter, moderate length, and strong adhesiveness with substrates then. Although the photocatalytic activity of Rh B degradation on TNTAs prepared in glycol and DMSO is higher than those prepared in glycerol, their convenience of recycling and recovery shows the opposite. The optimality condition of anodic oxidation for TNTAs with good morphology and photocatalytic performance was present, which may have potential application in the synthesis of composite nanoarrays.