This work presented a new approach to fabricate polymer nanocomposites films with nanofiber structures from solution blends of poly(vinyl alcohol) + octadecyl amine-montmorillonite (ODA-MMT) (matrix) with poly(N-vinylpyrrolidone) + ODA-MMT (partner-1), poly(N-vinylpyrrolidone-alt-maleic anhydride) ((poly(VP-alt-MA)) + (ODA-MMT) (partner-2) and their silver (Ag)-carrying polymer complexes by electrospinning. Chemical and physical structures, surface morphologies, thermal behaviors, electrical conductivity and thermal resistance parameters of nanofiber structures were investigated. Poly(VP-alt-MA) was used both as a crosslinker and a donor of the hydrophilic groups such as -COOH and -NH-C=O amide from pyrrolidone ring. Reactive poly(VP-alt-MA), in situ generated Ag nanoparticles (AgNPs) and original partner polymer had an significant effect on the morphology and diameter distribution of nanofibers. High and excellent conductive behaviors were observed for the homopolymer and copolymer of VP based fiber structures, respectively. Upon successive chemical cross-linking of the nanofiber structures by reactive partner copolymer, the conductivity of nanofiber films as electro-active platforms dramatically increased to 3.90 . 10(-2) S.cm(-1) at room temperature. Comparative analysis results also indicated that electrical properties strongly depended on the loaded reactive organoclay and in situ generated AgNPs.