Parylene films loaded with TiO2 are reported as hotocatalysts in azo dye discoloration processes. The TiO2 loading of the parylene film was 0.32% (w/w) and the amount of TiO2 on the film was about two orders of magnitude below the TiO2 added in suspension to discolore the same solution of Methyl Orange used as a probe. The parylene/TiO2 films showed a similar activity in the presence of O2 or H2O2 during the discoloration of dyes. This shows the efficient role of O2 as $e_{cb}^-$ scavenger. The photonic efficiency of the parylene/TiO2 film during the Methyl Orange discoloration was 0.04. Based on X-ray photoelectron spectroscopy (XPS) data, the TiO2 particles loaded on the parylene film were shown to be at first encapsulated in the polymer. After the encapsulation is broken, the TiO2 particles are fully exposed to the dye solution. The lack of surface intermediates like C-residues, N and S-species after the photocatalytic process implies an efficient decomposition of the dye at the catalyst interface. During the dye degradation carbonates and carboxylates were detected by XPS and Fourier transform infrared spectroscopy (FTIR) disappearing at the end of the discoloration process. Evidence is presented during the photocatalysis for the formation of a composite parylene/TiO2 film. The formation of this composite involves surface modification of parylene (partial lost of chlorine) in the outermost surface layer with concomitant densification of the TiO2 particles on the parylene film. The parylene film presented a side with high rugosity and one with low rugosity attaching different amounts of TiO2 in each case as observed by transmission electron microscopy (TEM).