In order to increase the applicability of photocatalysis in treating offshore produced water (OPW), an immobilized catalyst was introduced into the UV irradiation system and its performance on the degradation of organic compounds in OPW was evaluated. Naphthalene was selected as the target pollutant owing to its abundance in produced water and its chemical property as a typical polycyclic aromatic hydrocarbon. Aeroxide® P25 nano-scale TiO2 powder was immobilized on glass slides by a heat attachment method and its photocatalytic capacity was compared to that of the original powder in terms of naphthalene removal efficiency. The results of adsorption showed that the reduction of catalysts’ surface area by immobilization was similar to that by agglomeration. The photocatalytic reaction rate constants in the homogeneous and immobilized systems were 0.00219 min−1 and 0.00305 min−1, respectively, indicating that the immobilized catalyst had a better performance in photo-oxidation. The fouling of catalyst surface during the irradiation process came from the deposition of insoluble particles, organic matter, and the scaling of calcium. The immobilization of catalysts was more resistant to the substrate effects of OPW, indicating a promising alternative in treating OPW.