To optimize the interface of the catalyst layer (CL) and gas diffusion layer (GDL) in polymer electrolyte membrane fuel cells (PEMFCs), microporous layers (MPLs) with different decorative patterns were prepared. Carbon paper treated with polytetrafluoroethylene was used as a substrate for the coating of MPLs. To accelerate water removal and gas permeation, ammonium chloride was utilized to improve the porous structure of MPLs. Owing to the recrystallization and pyrolysis of ammonium chloride with different contents, the surface of MPLs exhibited point-, line-, and flowerlike patterns. Membrane electrode assemblies (MEAs) were assembled to evaluate the performance of MPLs with different decorative patterns. From measurements, an MEA containing a porosity-graded MPL (MPL-G) with a flowerlike pattern exhibited the best electrochemical performance. It is because that graded porosity accelerates the removal of excessive water. The flowerlike pattern facilitates the diffusion of the reactant gas at the interface of the catalyst layer and MPL. With the measurement of segmented cell technology, such MEAs revealed an improved redispersion of reactant gases. Furthermore, the produced water was compressed to the gas outlet, providing a larger active region for reaction. These results indicate that pattern design of MPLs is a promising strategy to improve the mass-transfer efficiency at the interface of the catalyst layer and gas diffusion layer.