This article presents preparation of poly (vinylidene fluoride-co-hexafluoropropylene) (PVdF-co-HFP) and polybenzimidazole (PBI) blend electrospun nanofiber (PVFP-BI) films from N,N'-dimethyl acetamide (DMAc)/acetone mixture solutions. Using the PVFP-BI nanofiber film (thickness similar to 13-15 pm) as a supporting material for impregnating Nafion resin solution, Nafion/PVFP-BI composite membranes (thickness 50 gm) are prepared and direct methanol fuel cell (DMFC) tests are performed. Better DMFC performance of the Nafion/PVFP-BI composite membrane than the commercial Nafion-117 (thickness 175 gm) and Nafion-212 (thickness 50 gm) membranes when blending with 5-10 wt.% of PBI in the PVFP-BI nanofiber support film is demonstrated. (C) 2014 Elsevier B.V. All rights reserved.