A rectangular recycling photo-bioreactor using glucose oxidase (GOx) immobilized on TiO2/polyurethane (PU) was developed as a novel coupling of photodegradation and enzymatic process. This method was tested for removal of Acid Orange 7 (AO7), as a model pollutant. High efficiency of decolorization (>99%) was achieved after 22min using the GOx/TiO2/PU photo-biocatalyst. Roles of various processes including photodegradation (TiO2/PU), enzymatic process (GOx/PU) and a coupling of photocatalytic–enzymatic (GOx/TiO2/PU) process were investigated in the presence and absence of UV light. All the experiments were performed in a circulation photoreactor equipped with a 6W UV lamp with rate of 5mL/min.