The emergence of non-biodegradable and persistent compounds in European surface waters calls for the development of innovative advanced water treatments. Therefore, this work aimed to assess the performance of a slurry photocatalytic membrane reactor to treat secondary wastewater effluent polluted by anticancer drugs. Results show that the 100 kDa Al2O3 membrane effectively rejected TiO2 catalyst particles. Furthermore, stable water permeabilities and separation properties were observed during 150 h in secondary wastewater under optimized operating conditions. However, significant deterioration of photocatalytic degradation rates were obtained in real effluent when compared to laboratory grade water experiments. An innovative matrix filtration methodology developed in this study permitted to conclude that the negative effects of real effluent were principally imputed to ions present in the real matrix. This study concluded that the photocatalytic membrane reactor is a promising technology for advanced water treatment, but still requires the development of a catalyst to operate on real effluents.