To achieve high proton conduction ability, we report here a novel and facile strategy to construct dual interfacial proton-conducting pathways in the platform of nanofibrous composite membranes (NFCMs) by mixing sulfonated halloysite nanotubes (SHNTs) with chitosan (CS) matrix and then incorporating them into the pores of sulfonated poly (ether ether ketone) (SPEEK) nanofiber mat. In such a way, two distinct interfacial pathways are created at SPEEK/CS and CS/SHNTs interfaces, on which ordered acid base pairs (-SO3- center dot center dot center dot +H3N-) are formed. And the strong electrostatic attractions endow NFCMs with enhanced structural stabilities by regulating polymer chain mobility and stacking. The dual-interfacial proton-conducting pathways confer ultrafast proton conduction on NFCM under both hydrated and anhydrous conductions via Grotthuss mechanism. Especially, CS/SPNIF/SHNTs-5 achieves remarkable conductivities of 117.7 mS cm(-1) under 90 degrees C and 100% RH, and 19.95 mS cm(-1) at 100 degrees C and 0% RH. Benefiting from the structural stability, the as-prepared NFCMs display excellent conduction stability for promising long-term operation. Moreover, to verify the universality of this nanostructured-transfer pathway, another kind of NFCM is fabricated using polydopamine modified nanofiber mat bearing numerous polydopamine nanoparticles. SPEEK is chosen as polymer matrix and incorporated into the mat to prepare the NFCMs, which also display expected efficient proton transfer behaviors. (C) 2016 Elsevier B.V. All rights reserved.