Plasma grafting is employed to prepare alkaline anion-exchange membranes in this study. The attenuated total reflection Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy and thermo gravimetric analysis demonstrate that the benzyltrimethylammonium cationic groups are successfully introduced into the polyvinyl chloride matrix via plasma grafting, quaternization and alkalization. The plasma-grafted alkaline anion-exchange membrane exhibits a satisfactory ionic exchange capacity (1.01mmolg −1 ), thermal stability, mechanical property, ionic conductivity (0.0145Scm −1 ) and methanol permeability (9.59×10 −12 m 2 s −1 ), suggesting a great potential for application in direct alcohol fuel cells. The open circuit voltage of air-breathing ADAFC using plasma-grafted alkaline anion-exchange membrane is 0.796V with 1M EtOH solution at ambient temperature.