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The micro-porous polymer electrolytes membranes(PEMs), notably electro-spun fiber mats, have been suggested to give an improved ionic conductivity. However, the mat-type PEMs have a poor mechanical and dimensional stability because of their inevitable porous nature. In this study, we suggest a new PEM system based on poly(vinylidene fluoride)(PVdF) mats, which can overwhelm such shortcomings of the porous mats by introducing another component, poly(4-vinyl pyridine)(P4VP), into the mats. The tensile strength of PVdF/P4VP membrane was considerably improved compared with that of pristine PVdF membrane under dry and wet conditions. The ionic conductivity was also improved by about 10 times than that of PVdF mat. A micro- to nano-size gap was formed at the interfaces between PVdF nanofiber and P4VP, and this may act as a channel for fast ion transportation under wet condition.