In this study, the degradation of naphthalene in water was performed via photocatalysis with two different configurations: UV-irradiated TiO2 deposited on cellulosic tissue and photocatalytic luminous textiles. The photocatalytic performance of these configurations was evaluated in terms of pollutant removal and mineralization yield. Moreover, the influence of key operating parameters, such as the initial pollutant concentration, solution turbidity, the number of tissues, and the type of irradiation, was investigated. The results showed a complete removal of 8 mg/L of naphthalene with photocatalytic luminous textiles after 4 h of UV irradiation, with a mineralization yield of 80%. The impact of the turbidity shows that at 90 NTU, reductions in photocatalytic activity of 30% and 10% were recorded for the UV-irradiated TiO2 deposed on cellulosic tissue and photocatalytic luminous textiles, respectively. The reactive oxygen species (ROS) concentrations were monitored during photocatalysis to better understand the contribution of each active species in the mechanism reaction of naphthalene oxidation. The results show that the hydroxyl radical (•OH) is responsible for 70% of pollutant oxidation. A scaling up of the water treatment with photocatalytic luminous textiles was performed. The extrapolation confirmed the same trends observed at the laboratory scale in terms of degradation and mineralization.