Polyvinyl alcohol/Poly-aniline/Vanadium Oxide nanocomposite-based macroscopic fibers have been generated by using a redox reaction addressed while performing an extrusion shaping process. The resulting composites have been thoroughly characterized via a large set of techniques such as SEM, SAXS, XRD and FTIR, in order to determine aniline effects over final materials' structures and properties. Thus, the perturbation of the preferential orientation of the V2O5 nano-ribbons toward the fiber main axis, induced by aniline Red-ox intercalation, has been observed. Also, the partial reduction of V5+ species to V4+ ones, due to the strongly oxidizing character of the first ones toward aniline, has been revealed by Electron Spin Resonance (ESR). Moreover, these fibers are able to detect 5 ppm of ethanol within 3-5 seconds at 42 °C, and possess a toughness of 12 J.g-1.