A new material based on crosslinked poly(vinylbenzyl chloride) (PVBC) with a macromolecular crosslinker is synthesized and employed as the membrane for anion exchange membrane fuel cells (AEMFCs). PVBC is used as the hydroxide conducting polymers, while poly(vinyl acetal) (PVAc) containing dimethylamino groups plays the role as macromolecular crosslinker and the supporting matrix simultaneously. Fourier transform infrared (FT-IR) absorption spectra and X-ray photoelectron (XPS) spectra prove successful crosslinking between PVBC and PVAc. The crosslinked membrane shows hydroxide conductivity larger than 0.01 S cm(-1) at room temperature, and the swelling by water at elevated temperature is suppressed. The H-2/O-2 AEMFC using the crosslinked membrane shows a peak power density (P-max) of 124.7 mW cm(-2) at 40 degrees C, and the decrease of the open circuit voltage (OCV) of the fuel cell is negligible under continuous OCV conditions for 120 h. All the results indicate that the crosslinking with a macromolecular crosslinker may be a promising strategy to fabricate anion exchange membrane for the application in the AEMFCs. (C) 2013 Elsevier B.V. All rights reserved.