Granular activated carbon (GAC) was added over the membrane cathode to expand its size. GAC expanded cathode coupled MFC/MBR system was studied. ORR pathways were 4e− on GAC and 2e− on FeOOH/TiO2/GAC. Formation and decomposition of H2O2 was catalyzed by loaded FeOOH/TiO2 on GAC. Oxidative tetracycline hydrochloride removal (90%) was realized by hydroxy radical.