Electrospun quaternized polyvinyl alcohol (Q-PVA) nanofibers are prepared, and a potassium hydroxide (KOH)-doped nanofiber mat demonstrates enhanced ionic conductivity compared with a dense Q-PVA film with KOH doping. The Q-PVA composite containing 5.98% electrospun Q-PVA nanofibers exhibits suppressed methanol permeability. Both the high conductivity and suppressed methanol permeability are attributed to the quasi-coaxial structure of the electrospun nanofibers. The core of the fibers exhibits a more amorphous region that forms highly conductive paths, while the outer shell of the nanofibers contains more polymer crystals that serve as a hard sheath surrounding the soft core. This shell induces mass transfer resistance and creates a tortuous fuel pathway that suppresses methanol permeation. Such a Q-PVA composite is an effective solid electrolyte that makes the use of alkaline fuel cells viable. In a direct methanol alkaline fuel cell operated at 60 degrees C, a peak power density of 54 mW cm(-2) is obtained using the electrospun Q-PVA composite, a 36.4% increase compared with a cell employing a pristine Q-PVA film. These results demonstrate that highly conductive coaxial electrospun nanofibers can be prepared through a single-opening spinneret and provide a possible approach for high-performance electrolyte fabrication. (C) 2015 Elsevier B.V. All rights reserved.