The developmentofefficient hybridmembranesforhightemperatureProtonExchangeMembraneFuelCell (PEMFC)iscurrentlyunderinvestigation.Here,weshowthattheelectrospinningprocesscombinedwith thesol-gelchemistryconducestomembraneswithprotonicconductivitysimilartoNafion, athightemperatureundertherelativehumidityof90%,andwithanisotropicmechanicalpropertiesduetothepresence oflong-rangeanisotropicobject.Theelectrospunmembranes’ morphology isalsohighlyde-pendent onthesol-gelchemistry(with/withoutadditives)aswellastheprocessingparametersin-cluding relativehumidity,appliedelectrical field, temperature,rotatingelectrode'sspeed… Our hybridfibers arebasedonpoly(vinylidene fluoride-hexafluoropropylene)(PVDF-HFP)/SO3H-silica networksthat combinestheabilitytomimicthenanostructuralphaseseparationobservedinhydratedNafionwith majorfeature,thatis,arrayoforientatedionicnanochannelsintermingledwithinalocallyalignedpolymer,whereprotoncaneasilydiffuseinthistubularnanostructure.