Passive direct methanol fuel cells (DMFCs) operating with neat methanol can achieve the maximum system energy density. However, the anodic methanol oxidation reaction requires reactant water, which is completely supplied by water generated at the cathode, causing the system to experience a critical issue known as water starvation. A solution to this problem involves increasing the water recovery flux to meet the rate of water consumption of the anodic reaction, and increase the local water concentration as high as possible at the anode catalyst layer (CL) to improve the anodic kinetics. In the present work, a new microporous layer (MPL) consisting of a hydrophilic layer and a hydrophobic layer is proposed. The purposes of these two layers are to, respectively, trap and retain water and to create capillary pressure to prevent water loss. Our experiments have shown that the use of this novel MPL at the anode and cathode can increase the rate of water recovery and water retention, resulting in an increase in the local water concentration. As a result, the use of this dual-layer MPL to either electrode of a passive DMFC operating with neat methanol leads to a significant performance boost. (C) 2015 Elsevier B.V. All rights reserved.