Nanofibers have attracted attention in the field of thermoelectric (TE) because of their remarkable properties; abundance, lightweight with the high-surface area-to-volume ratio, low thermal conductivity, mechanically stable, and non-toxic. In applications, like TE wearable device for energy harvesting, development of new composite nanofibers holds more significant potential with the targeted specifications. In our research, we have investigated for the first-time fiber nanocomposites for the application of wearable power generator in terms of TE energy. The electrospun technique attracts in the development of nanostructured materials in the field of thermoelectric power generation. The significance of this paper is to flourish the wearable device materials of 1D vanadium oxide/tin oxide (V2O5/SnO2) composite nanofibers synthesized using sol-gel method followed by electrospinning process. The structural and morphology properties of SnO2 fibers belong to tetragonal structure and nanocomposite relates to tetragonal (SnO2) and orthorhombic (V2O5) structure, diameter in the range of 100-400 nm. The high-surface area to volume ratio of nanofiber allowed more significant phonon scattering and enhance the efficiency. The nanofiber exhibits the outstanding TE properties of the Seebeck coefficient and power factor of 20-100 V/K and 0.3-1.6 mu W/K(2)m at room temperature to 400 K, which is the highest among the fiber SnO2 and its composites. The nanofibers integration on wearable devices paves the way towards ultralight, thermally stable, tunable density and mechanically flexibile are unique, where nanocomposite offers a new opportunity to thermoelectric applications. Schematic representation of fabrication process PVA-SnO2 NFs and PVA-V2O5/SnO2 NCF.