Gallium oxide (Ga2O3) thin films were fabricated on glass substrates using a combination of chemical bath deposition and post-annealing process. From the field-emission scanning electron microscopy and x-ray diffraction results, the GaOOH nanorods precursors with better crystallinity can be achieved under higher concentrations (≥0.05 M) of gallium nitrate (Ga(NO3)3). It was found that the GaOOH synthesized from lower Ga(NO3)3 concentration did not transform into α-Ga2O3 among the annealing temperatures used (400–600 °C). Under higher Ga(NO3)3 concentrations (≥0.05 M) with higher annealing temperatures (≥500 °C), the GaOOH can be transformed into the Ga2O3 film successfully. An α-Ga2O3 sample synthesized in a mixed solution of 0.075 M Ga(NO3)3 and 0.5 M hexamethylenetetramine exhibited optimum crystallinity after annealing at 500 °C, where the α-Ga2O3 nanostructure film showed the highest aspect ratio of 5.23. As a result, the photodegeneration efficiencies of the α-Ga2O3 film for the methylene blue aqueous solution can reach 90%.