Colloidal polymer nanofibers as non-crystalline solid electrolytes were fabricated by using solution blends of polyvinyl alcohol/octadecyl amine-montmorillonite, alternating copolymer of itaconic anhydride with 2-vinyl-1,3-dioxalane and their Ag-carrying complexes by electrospinning. Chemical-physical structures, morphology, thermal and electrical properties of nanofiber electrolytes were investigated to evaluate their influences on the conductivity and resistance parameters. Successful chemical cross-linking of PVA matrix by reactive partner copolymer was observed via ring-opening esterification/cross-linking. A covalence bridge of partner copolymer between PVA macromolecules not only reinforced the network but also provided extra ion charged sites. Effects of alternating copolymer fraction, organoclay, in situ generated silver nanoparticles, and structural factors on the conductivity of nanofiber thin films were estimated. Conductivity and resistance parameters strongly depended on temperature, conduct time, morphology and in situ structural rearrangements during electrospinning. Addition of reactive organoclay and Agcarrying copolymer significantly improved the conductivity due to enhancing nanofiber structures with carboxylate ion charge sites. (C) 2015 Elsevier B.V. All rights reserved.