The present work demonstrates the formation of self-aligned nanoporous architecture of gallium oxide by anodization of gallium metal film controlled at -15 degrees C in aqueous electrolyte consisting of phosphoric acid. SEM examination of the anodized film reveals that by adding ethylene glycol to the electrolyte and optimizing the ratio of phosphoric acid and water, chemical etching at the oxide/electrolyte interfaces can be controlled, leading to the formation of aligned nanotubular oxide structures with closed bottom. XPS analysis confirms the chemical composition of the oxide film as Ga2O3. Further, XRD and SAED examination reveals that the as-synthesized nanotubular structure is amorphous, and can be crystallized to beta-Ga2O3 phase by annealing the film at 600 degrees C. The nanotubular structured film, when used as photoanode for photoelectrochemical splitting of water, achieved a higher photocurrent of about two folds than that of the nanoporous film, demonstrating the rewarding effect of the nanotubular structure. In addition, the work also demonstrates the formation of highly organized nonporous Ga2O3 structure on a nonconducting glass substrate coated with thin film of Ga-metal, highlighting that the current approach can be extended for the formation of self-organized nanoporous Ga2O3 thin film even on nonconducting flexible substrates.