Novel and highly durable alkaline anion-exchange membranes, PVA/PDDA-OH-, are synthesized using a combined thermal and chemical cross-linking method. In the synthesis, poly(vinyl alcohol) (PVA) is used as polymer matrix and poly(diallyldimethylammonium chloride) (PDDA) as anion charge carriers. The resulting membrane exhibits a high hydroxide conductivity of 0.025 S cm(-1) at a polymer composition PVA/PDDA being 1:0.5 by mass. A promising H-2/O-2 fuel cell peak power density of 32.7 mW cm(-2) is reached for MEA fabricated with this PVA/PDDA-OH- at 25 degrees C. The membrane also shows a strong alkaline stability in 8 M KOH at 80 degrees C for 360 h. This is considered a new record for the fully cation-free hydrocarbon membranes for the use in alkaline fuel cell, seeing that PVA/PDDA-OH- is made simply of aliphatic skeletons. (C) 2013 Elsevier B.V. All rights reserved.