In this study, polyethylene glycol (PEG) was tested as an alternative polymer to improve the coating of TiO₂ particles onto optical fibres. The addition of PEG helped dispersing effectively the particles in solution to control their deposition and therefore achieving better properties of the coating film. Results showed that PEG increased the effectiveness of the coating and the prepared fibres showed better performance for the removal of methylene blue (MB). This was attributed to the morphological changes induced by PEG. EDX mapping of the fibre surface showed that the addition of PEG lead to a better coverage of the fibre surface; increasing the active surface area for subsequent photocatalytic degradation. This study also showed that the light intensity, pH and initial concentration of MB have a significant influence. Finally, it was demonstrated that the coatings using PEG were better ordered and structured; showing a distinct layer-by-layer deposition.