In this study photoelectrocatalytic technology has been combined with fuel cell technology in an attempt to provide a stand alone water polishing device to be applied to the water purification industry. Tungsten trioxide was chosen as the photoelectrocatalyst to be applied to the fuel cell membrane electrode assembly (MEA). In this thesis two possible WO₃-based photoanodes were studied. Firstly a Nafion-loaded WO₃ photoanode utilising the state of the art proton conductor Nafion in the MEA. The second WO₃-based photoanode was synthesised by a sol-gel method with a view to being directly sintered onto a not yet developed solid state MEA containing a proton conductive glass. In both methods electrochemical studies were undertaken with both WO₃ based photoanodes deposited on fluorine doped tin oxide glass (FTO). The WO₃ catalysts were studied by X-ray diffraction, Raman spectroscopy, Nitrogen adsorption and UV-visible spectroscopy. Electrochemical studies included cyclic voltametry and linear sweep voltametry under illumination to ascertain the photocurrent densities of the photoanodes and hence their ability to degrade water borne contaminants. The underlying materials properties were explored as well as the nature of the deposition to gain insight into the mechanisms responsible for effective photoelectrocatalytic activity. The Nafion-loaded WO₃ was applied to a Nafion membrane based MEA and utilised in a photoelectrocatalytic fuel cell. This was studied for possible application under self sustaining conditions for application in the water industry.