Anion exchange membranes (AEMs) have attracted great attention due to their irreplaceable role in platinum-free fuel cell applications. The majority of AEM preparations have been performed in two steps: the grafting of functional groups and quaternization. Here, we adopted a simpler, more eco-friendly approach for the first time to prepare AEMs by atmospheric-pressure plasma-grafting. This approach enables the direct introduction of anion exchange groups (benzyltrimethylammonium groups) into the polymer matrix, overcoming the need for toxic chloromethyl ether and quaternization reagents. Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy and H-1 NMR spectroscopy results demonstrate that benzyltrimethylammonium groups have been successfully grafted into the cardo polyetherketone (PEK-C) matrix. Thermogravimetric analysis reveals that the plasma-grafting technique is a facile and non-destructive method able to improve the thermal stability of the polymer matrix due to the strong preservation of the PEK-C backbone structure and the cross-linking of the grafted side chains. The plasma-grafted PG-NOH membrane, which shows satisfactory alcohol resistance (ethanol permeability of 6.3 x 10(-7) cm(2) s(-1)), selectivity (1.2 x 10(4) S s cm(-3)), thermal stability (safely used below 130 degrees C), chemical stability, anion conductivity (7.7 mS cm(-1) at 20 degrees C in deionized water) and mechanical properties is promising for the construction of high-performance fuel cells. (C) 2014 Elsevier B.V. All rights reserved.