Highly stable hydroxyl anion conducting membranes have been developed using poly(vinyl alcohol) (PVA) as matrix by incorporation of poly(acrylamide-co-diallyldimethylammonium chloride) (PAADDA) as anion charge carriers. In order to clarifying the cross-linking effect on membrane performances, two series of PVA/PAADDA membranes were prepared by direct and indirect chemical cross-linking ways, and have been characterized in detail at structural and hydroxyl ion (OH − ) conducting property by FTIR spectroscopy, thermal gravity analysis (TG), scanning electron microscopy (SEM), water sorption, ion exchange capacity and alkaline resistance stability. The OH − conductivity of the membranes increased with increasing the content of PAADDA in polymer and temperature, and reached 0.74–12 mS cm −1 with direct cross-linking way and 0.66–7.1 mS cm −1 with indirect cross-linking way in the temperature range 30–90 °C. The membranes are found to have the same IEC values but the membranes with direct cross-linking way showed higher water uptake than that with indirect cross-link one. Both membranes showed the thermal stability above 200 °C, and can integrity in 100 °C hot water and methanol solution, where the swelling are better suppressed as high dense chemical cross-linkages in PVA network. Very low methanol permeability (from 1.82 × 10 −7 to 3.03 × 10 −7 cm 2 s −1 ) in 50% methanol solution was obtained at 30 °C. Besides, the chemical stability in 80 °C, 6 M hot alkali conditions and long-term stability of 350 h in 60 °C hot water revealed that the PVA/PAADDA membranes are promising for potential application in alkaline fuel cells.