The proton exchange membrane based on polyetheretherketone was prepared via two steps of cross-linking. The properties of the double cross-linked membrane (water uptake, proton conductivity, methanol permeability and thermal stability) have been investigated for fuel cell applications. The prepared membrane exhibited relatively high proton conductivity, 3.2 x 10(-2) S cm(-1) at room temperature and 5.8 x 10(-2) S cm(-1) at 80 degrees C. The second cross-linking significantly decreased the water uptake of the membrane. The performance of direct methanol fuel cell was slightly improved as compared to Nafion (R) 117 due to its low methanol permeability. The results indicated that the double cross-linked membrane is a promising candidate for the polymer electrolyte membrane fuel cell, especially for the direct methanol fuel cell due to its low methanol permeability and high stability in a methanol solution. Copyright (C) 2011, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.