Crosslinked poly(vinyl alcohol) (PVA) membranes were prepared at various crosslinking temperatures using poly(acrylic acid-co-maleic acid) (PAM) containing different PAM contents. The thermal properties of these PVA/PAM membranes prepared at various reaction temperatures were characterized using differential scanning calorimetry (DSC). The proton conductivity and methanol permeability of PVA/PAM membranes were then investigated as PAM content was varied from 3 to 13 wt%. It was found that the proton and methanol transport were dependent on PAM content in their function both as crosslinking agent and as donor of hydrophilic -COOH groups. Both these properties decreased monotonously with increasing PAM concentration. The proton conductivities of these PVA/PAM membranes were in the range from 10-3 to 10-2S/cm and the methanol permeabilities from 10-7 to 10-6cm2/sec. In addition, the effect of operating temperature up to 80 oC on ion conductivity was examined for three selected membranes: 7, 9 and 11 wt% PAM membranes. Ion conductivity increased with increasing operating temperature and showed and S/cm at 80 oC, respectively. The effects of crosslinking and ionomer group concentration were also examined in terms of water content, ion exchange capacity (IEC), and fixed ion concentration. In addition, the number of water molecules per ionomer site was calculated using both water contents and IEC values. With overall consideration for all the properties measured in this study, 7~9 wt% PAM membrane prepared at 140 oC exhibited the best performance. These characteristics of PVA/PAM membranes are desirable in applications related to the direct methanol fuel cell (DMFC).