This research reports on Vis- and solar-active photocatalytic bi-layered films of TiO2 (layer 1) and a composite with TiO2 matrix and graphene oxide or reduced graphene oxide filler (layer 2) obtained by coupling two methods: spray pyrolysis deposition followed by spraying a diluted sol. The thin films crystallinity degree, surface morphology and elemental composition were recorded and the composites were tested in photo-degradation processes, using the standard 10 ppm methylene blue solution, under simulated UV + VIS irradiation conditions using an irradiance measured to be close to the natural one, in continuous flow process, at demonstrator scale; these results were compared with those recorded when using low irradiance values in static regime. The effect of the increase in the graphene oxide content was investigated in the concentration range 1.4%w...10%w and was found to increase the process efficiency. However, the photocatalytic efficiencies increased only by 15% at high irradiance values compared with the values recorded at low irradiance as result of the electron-hole recombination in the composite-thin film. Similar experiments were run using composites having reduced graphene oxide as filler. The interfaces developed between the matrix and the filler were discussed outlining the influence of the filler’s polarity. The thin films stability in aqueous medium was good, confirmed by the results that outlined no significant differences in the surface aspect after three successive photocatalytic cycles.