The low ionic conductivity and low thermal stability of conventional quaternary ammonium group functionalized anion-exchange membranes (AEM) are two key parameters that limit the performance of AEM direct ethanol fuel cells (AEM DEFCs). The present work is to address these issues by synthesizing crosslinked poly (vinyl alcohol)/layered double hydroxide (PVA/LDH) hybrid membranes with solution casting method. The experimental results indicate that incorporating 20 wt.% LDH into the PVA resulted in not only a higher ionic conductivity, but also a lower ethanol permeability. The performance test of the DEFC using the PVA/LDH hybrid membrane shows that the fuel cell can yield a power density of 82 mW cm −2 at 80 °C, which is much higher than that of the AEM DEFC employing the quaternary ammonium group functionalized membrane. A constant current discharge test shows that the PVA/20LDH membrane can be operated stably at relatively high temperatures.