We have developed an innovative thin-film nanocomposite membrane that contains cellulose acetate (CA) with small amounts of TiO2-decorated graphene oxide (GO) (ranging from 0.5 wt.% to 2 wt.%) sandwiched between two polytetrafluoroethylene (PTFE)-like thin films. The PTFE-like films succeeded in maintaining the bulk porosity of the support while increasing the thermal and chemical robustness of the membrane and boosting the catalytic activity of TiO2 nanoparticles. The membranes exhibited a specific chemical composition and bonding, with predominant carbon–oxygen bonds from CA and GO in the bulk, and carbon–fluorine bonds on their PTFE-like coated sides. We have also tested the membranes’ photocatalytic activities on azithromycin-containing wastewaters, demonstrating excellent efficiency with more than 80% degradation for 2 wt.% TiO2-decorated GO in the CA-GO-TiO2/PTFE-like membranes. The degradation of the azithromycin formulation occurs in two steps, with reaction rates being correlated to the amount of GO-TiO2 in the membranes.