Using solar-powered water electrolysis systems for hydrogen generation is a key decision for the development of a sustainable hydrogen economy. A facile approach is presented in the present investigation to improve the solar-powered photoelectrochemical performance of water electrolysis systems by synthesising well-aligned and highly ordered TiO₂ nanotube films without bundling through the electrochemical anodisation technique. Herein, geometrical calculations were conducted for all synthesised TiO₂ nanotubes, and determination of the aspect ratio (AR) and geometric surface area factor (G) was achieved. On the basis of the collected data, well-aligned TiO₂ nanotubes with an AR of approximately 60 and G of approximately 400 m² ·g-1 were successfully formed in an electrolyte mixture of ethylene glycol with 0.3 wt% NH4F and 5 wt% H₂O₂ at 40 V for 60 min. The nanotubes were subsequently annealed at 400 °C to form anatase-phase TiO₂ nanotube films. The resultant well-aligned and highly ordered TiO₂ nanotube films exhibited a photocurrent density of 1.5 mA · cm-2 due to a large number of photo-induced electrons moving along the tube axis and perpendicular to the Ti substrate, which greatly reduces interfacial recombination losses.