The photocatalytic degradation of saturated aqueous solution of naphthalene and anthracene was studied over thin films of porous TiO2 particles on glass substrate, prepared by sol-gel process. Surface morphology and structural features were studied by SEM, TEM and Laser Raman Spectroscopy. These films have been found to be very efficient and the total photomineralisation of these organics to carbon dioxide and water occurs in air-equilibrated solution within 1 h. Concentration changes linearly with the illumination time, and high rate constants are obtained for the degradation of these organics. The pH of the solution changes with the irradiation time due to the formation of intermediate photoproducts, e.g., 5,8-dihydroxynaphthaquinone, and 9,10-anthraquinone, etc. Photodegradation mechanism and the detection of reaction intermediates have been discussed in details.