Water management is always one of the main problems of polymer electrolyte fuel cells performance enhancement because it dramatically influences oxygen transport resistance. Typically, the MPL coated GDL with strong hydrophobicity effectively prevents flooding between the catalyst layer and the MPL. To further improve PEFC performance, directly coating an extra hydrophilic MPL on the hydrophobic MPL coated GDL as double MPL can further promote performance. The double MPL using Nafion binder cannot provide enough hydrophilicity to lower the oxygen transport resistance. Combining utilization of the Nafion and TiO2 is efficacious in decreasing the breakthrough pressure and contact angle and ameliorating water drainage from the MEA so that the gas transport ability can be improved. Besides, the appropriate thickness of the double MPL was investigated to better design the double MPL coated GDL.