Novel alkaline anion-exchange membranes composed of chemically cross-linked poly(vinyl alcohol) modified quaternized hydroxyethylcellulose ethoxylate (PVA/QHECE) are prepared. The hydroxide conductivity (σ OH − ), water and methanol uptakes, ion exchange capacity (IEC), mechanical property, dimensional and alkaline stabilities of PVA/QHECE membranes are measured to evaluate their applicability in direct methanol alkaline fuel cells (DMAFC). The effects of cross-linking time, membrane composition and catalyst dosage (H + ) on membrane OH − conductivity are studied using AC impedance technique. FTIR, SEM and TG analysis are used for structural characterization of these membranes. It is found that the OH − conductivity of the membranes increases with temperature and reaches up to 7.5 × 10 −3 S cm −1 at 90 °C but no apparent changes on both water uptake and methanol uptake with temperature. The methanol permeability coefficients of the membranes are in the range of 1.26–1.72 × 10 −7 cm 2 s −1 at 25 °C. In addition, the PVA/QHECE membranes show the high alkaline stability in hot 6.0 M KOH at 80 °C without losing their integrity and OH − conductivity during a week of evaluation. The membrane electrode assembly (MEA) fabricated with PVA/QHECE (= 1:0.25 by mass) gives an initial power density of 4.6 mW cm −2 using 2.0 M methanol and 2.0 M KOH as the fuel and O 2 as oxidant at room temperature.