A unique type of nano-structured proton exchange membrane (PEM) has been fabricated through photo-polymerizing a bicontinuous microemulsion. This microemulsion is constituted by a polymerizable zwitterionic surfimer 3-((11-acryloyloxyundecyl)imidazoyl)propyl sulfonate (AIPS), 3-sulfopropylmethacrylate, potassium salt (SPM), acrylonitrile and water. As the resulting colloidal system maintains quasi-homogeneous state throughout the polymerization course, the inherent bicontinuous microemulsion structure was successfully transferred to the matrix of the polymer membrane. Such membranes are therefore composed of dual phase channels with ca. 1.5-2 nm of the hydrophilic channel breadth. This particular structural trait imparts to the membranes excellent proton conductivities of up to 10(-1) S cm(-1) as well as low methanol permeability. The DMFC single cell loaded with the demo PEM manifests ca. 20 mW cm(-2) of power output. The attributes of this PEM are elucidated from the bicontinuous structure of microemulsion. (c) 2007 Elsevier B.V. All rights reserved.