New types of triple-layer membranes were fabricated using multi-step impregnation of Nation in electrospun webs based on bead-free nanofibers of sulfonated poly(ether sulfone) (SPES). The results showed that the fabricated nanofiber-filled membrane owing to its reduced methanol permeability as well as sufficient proton conductivity and membrane selectivity can be used as a promising proton exchange membrane for direct methanol fuel cell (DMFC) applications. The single cell DMFC performance results revealed that the SPES nanofiber-based triple-layer membranes have higher electrochemical performance than commercial Nation membranes. (C) 2011 Elsevier B.V. All rights reserved.