The pollutant composition of landfill leachate is complex, and pollutant concentrations change greatly. Moreover, landfill leachates can easily penetrate into the soil and eventually pollute the ground water, which can cause environmental pollution and threaten human health. At present, landfill leachate treatment technology is still not mature. In this paper, the A/O-MBR (Anoxic–Aerobic Membrane Bioreactor) process is proposed to treat landfill leachate. To increase the hydrophilicity of the membranes and reduce the pollution of the membranes, the self-made TiO₂ nanoparticles were used to modify the ultrafiltration membranes (PVDF-2). Meanwhile, PVDF-2 composite membranes showed the best separation performance. The optimum operating parameters were determined by changing the concentration of the pollutants in the reactor and selecting the dissolved oxygen, pH, and hydraulic residence time. The results show that the optimum operating conditions of MBR are mixed liquor suspended solids (MLSS) = 3200 mg/L, DO = 1.5–2.5 mg/L in a nitrifying tank, DO = 0–0.5 mg/L in a denitrifying tank, pH = 7–8, and a hydraulic retention time (HRT) = 5 h. To reach the “Discharge Standard of Pollutants for Municipal Wastewater Treatment Plants” (GB18918-2002), the effluent of the MBR system further enters into the RO system. This work presents an environmentally friendly synthesis of TiO₂ nanoparticles and added into PVDF. The addition of self-made TiO₂ in PVDF membrane has improved the antifouling performance significantly, which has the potential for the treatment of landfill leachate.