Highly ordered TiO2 nanotube array electrodes were successfully fabricated by a two-step anodization method on Ti sheet substrates in an electrolyte composed of ammonium fluoride, deionized water, and glycol. The tube wall was smooth, and the average internal and external diameters, wall thickness, and tube length achieved were 80 nm, 90 nm, 10 nm, and 9 µm, respectively. X-ray diffraction and field emission scanning electron microscopy results revealed that the TiO2 nanotube arrays presented an amorphous structure. When calcined at 300 °C, the arrays crystallized into the anatase phase, and the crystallization degree of the oxide layer increased as the temperature rose. Calcinating at 400 °C did not obviously disrupt the porous structure of the highly ordered arrays. However, higher temperature enlarged the diameter of the nanotube array and roughened the tube wall. When the temperature reached 600 °C, the nanotube mouth broke because of the excessive stress, causing the oxide layer's thinness and nanotube mouth clogging. The photoelectric test showed that the electrode presented obvious photoresponse under 300-400 nm UV excitation (maximized at 360 nm). The degree of crystallization and the micro-structure of the oxide layer can significantly affect the photoelectric properties of the electrode. After calcination at 400 °C, the TiO2 nanotube arrays, with highly ordered tubular structure directly connected to the Ti substrate, can ensure the rapid transportation of photo-induced electrons to the Ti substrate, while the high crystallinity of the arrays can help reduce the defect density of the nanotube and extend the lifetime of the photo-induced carriers. The electrode showed the best photoelectric property, and the photocurrent intensity was maximized (29.6 µA). However, the calcination process with over-temperature resulted in substantial loss of the TiO2 oxide layer, mouth clogging, and a severe decline in the photoelectric properties.