In this study, the direct methanol fuel cell performance of Nafion®/poly(vinyl alcohol) (PVA) blend membranes at 5, 10, and 20wt% PVA (annealed at 230°C) was investigated at various methanol feed concentrations (2, 4, 8, and 16M) and compared to the performance of Nafion® 117 at similar membrane thicknesses and fuel cell conditions. For Nafion® 117, the maximum power density decreased three-fold when the methanol feed concentration increased from 2 to 16M. The Nafion®/PVA (5wt% PVA) blend membrane reveals a similar trend, however the decrease in power is only 26% compared to 47% when methanol concentration is increased from 2 to 8M. Furthermore, the maximum power density of the blend membrane (5wt% PVA) is higher than Nafion® 117 at 2, 4, and 8M methanol feed concentrations, while the maximum power density at 16M is comparable between the two membranes. Specifically, at 8M methanol, the maximum power density of the blend at 5wt% PVA is 33% higher than Nafion® 117. Blend membranes at higher PVA concentrations are noticeably lower in performance compared to Nafion® 117. Overall, fuel cell performance trends match observed transport property (proton conductivity and methanol permeability) trends.