Novel multifunctional colloidal polymer nanofiber electrolytes were fabricated by green reactive electrospinning nanotechnology from various water solution/dispersed blends of poly (vinyl alcohol-co-vinyl acetate) (PVA)/octadecyl amine-montmorillonite (ODA-MMT) as matrix polymer nanocomposite and poly(maleic acid-alt-acrylic acid) (poly(MAc-alt-AA) and/or its Ag-carrying complex as partner copolymers. Polymer nanofiber electrolytes were characterized using FTIR, XRD, thermal (DSC, TGA-DTG), SEM, and electrical analysis methods. Effects of partner copolymers, organoclay, in situ generated silver nanoparticles (AgNPs), and annealing procedure on physical and chemical properties of polymer composite nanofibers were investigated. The electrical properties (resistance, conductivity, activation energy) of nanofibers with/without NaOH doping agent were also evaluated. This work presented a structural rearrangement of nanofiber mats by annealing via decarboxylation of anhydride units with the formation of new conjugated double bond sites onto partner copolymer main chains. It was also found that the semiconductor behaviors of nanofiber structures were essentially improved with increasing temperature and fraction of partner copolymers as well as presence of organoclay and AgNPs in nanofiber composite.