In order to widen the market application of the polymer electrolyte fuel cell (PEFC), the output power of the PEFC system must be increased. One of the barriers is the cell voltage loss under high current density conditions. This is mainly caused by the deteriorated reactant mass transport, which is blocked by the water flooding at the catalyst layer (CL), microporous layer (MPL), and gas diffusion layer (GDL). Modifying the MPL coated on the GDL is an accessible way to provide better water management for PEFCs to elongate the operating range of the cell, so a novel MPL-coated GDL should be developed to realize the goal. Previously, we evaluated double MPL-coated GDLs, which coated a thin hydrophilic layer on the hydrophobic MPL-coated GDL in the through-plane direction. The extra hydrophilic layer was influential in promoting the introduction of water into the small pores of the hydrophobic MPL, enhancing the ability to reduce flooding, and the oxygen transport resistance under high humidity conditions can be declined.The present study evaluates a novel composite MPL that the hydrophobic and hydrophilic pores are randomly allocated in the same layer. Excess water is expelled from the hydrophilic pores while maintaining gas transport by the hydrophobic pores. To determine the appropriate hydrophobic and hydrophilic compositions, we first evaluated the most commonly used hydrophobic polytetrafluoroethylene (PTFE) binder, and the contact angle of PTFE-MPL was 136°. Polyvinyl alcohol (PVA) was chosen as the hydrophilic binder, and the contact angle of PVA-MPL was 105°. The slurry containing PTFE, PVA, carbon black, and distilled water was mixed using a mixer and then spread on the carbon paper substrate by a bar coating machine. The temperature was heated at 350°C to sinter the MPL on the substrate. However, the sintering temperature of PVA should be lower than 150°C, so the PVA in the composite MPL was burned and led to a similar contact angle as the PTFE-MPL. Meanwhile, the performance enhancement could not be obtained compared with a PTFE-MPL-coated GDL. Oppositely, when decreasing the sintering temperature to 150C°, the PTFE-PVA composite MPL demonstrated strong hydrophilicity with a small contact angle value, and the performance was exacerbated than the PTFE-MPL. Therefore, to coordinate the lower sintering temperature of PVA, polyvinylidene difluoride (PVDF) was selected as the hydrophobic binder. The contact angle of PVDF-MPL was 143°. After the PVA was preserved, the unexpectedly strong hydrophilicity was exhibited in PVDF-PVA composite MPL, aggravating the liquid water accumulation in the MPL and without performance improvement. Finally, the Nafion ionomer with relatively weak hydrophobicity was used for the composite MPL. As a hydrophilicity complement, titanium dioxide (TiO2) particles were added to the slurry to control hydrophilicity. The contact angle of Nafion/TiO2-MPL was 113°. Similarly, the Nafion/TiO2-PVDF composite MPL indicated a contact angle of 114°, and the water permeability test proved that separate hydrophobic and hydrophilic pores were generated.The oxygen transport resistances were measured based on the limiting current density values of polarization curves to evaluate the ability of the MPL-coated GDL to reduce flooding under high humidity conditions. The active area of the MEA was 1.0 cm2, and the cell temperature was kept at 35°C. Pure hydrogen and diluted oxygen (2 vol% O2 and 98 vol% N2) gases were supplied at the anode and cathode, respectively, and the flow rates were set at 1000 cm3 min-1. The relative humidity of gases supplied to the anode and cathode was 200%RH, and the gas backpressure was set at zero. The oxygen transport resistance of the Nafion/TiO2-PVDF composite MPL-coated GDL was lower than that obtained with a commercial SGL-22BB GDL. Thus, an appropriate composite MPL-coated GDL effectively enhanced PEFC performance under high humidity conditions.