The development of efficient hybrid membranes for high temperature Proton Exchange Membrane Fuel Cell (PEMFC) is currently under investigation. Here, we show that the electrospinning process combined with the sol-gel chemistry conduces to membranes with protonic conductivity similar to Nafion, at high temperature under the relative humidity of 90%, and with anisotropic mechanical properties due to the presence of long-range anisotropic object. The electrospun membranes’ morphology is also highly dependent on the sol-gel chemistry (with/without additives) as well as the processing parameters including relative humidity, applied electrical field, temperature, rotating electrode's speed… Our hybrid fibers are based on poly(vinylidene fluoride-hexafluoropropylene) (PVDF-HFP)/ SO3H-silica networks that combines the ability to mimic the nano structural phase separation observed in hydrated Nafion with major feature, that is, array of orientated ionic nano channels intermingled within a locally aligned polymer, where proton can easily diffuse in this tubular nanostructure.