Novel multifunctional polymer nanofiber electrolytes with covalence crosslinked structures from various solution blends of reactive intercalated poly(vinyl alcohol)/octadecylamine montmorillonite (as a matrix polymer), poly(maleic anhydride-alt-methyl vinyl ether) (as a partner polymer) and their NaOH-absorbing and Ag-carrying polymer complexes were fabricated via electrospinning. Chemical, physical, morphological, and electrical properties of nanofiber structures were investigated by FTIR, XRD, SEM, and electrical analysis methods. Ag precursors in fiber composites significantly improved phase separation processing, fiber morphologies, diameter distributions, and electrical properties of the fibers. In situ generation of Ag nanoparticles and their distribution on nanofiber surfaces during fiber formation occurred via complex formation between silver cations and electronegative functional groups from both matrix and partner polymers as stabilizing/reducing agents. Electrical resistance and conductivity strongly depended on matrix/partner polymer ratios and absorption time of NaOH solution on nanofibers. Addition of NaOH changed the electrical properties of fiber structures from almost dielectric state to excellent conductivity form. The fabricated unique nanofiber electrolytes are promising candidates for applications in power and fuel cell nanotechnology, electrochemical, and bioengineering processes as reactive semiconductive platforms. (C) 2015 Society of Plastics Engineers