The present work is focused on the preparation and characterization of SnO2-based fibers suitable for gas sensing application. The pure SnO2 fibers were synthesized together with Fe3+-doped and Fe3O4 nanoparticles-doped SnO2 fibers by needle-less electrospinning technique and followed the calcination process. Fe modification of SnO2 fibers was prepared by the simple addition of Fe(NO3)(3).9H(2)O or Fe3O4 nanoparticles to the spinning solution. Subsequently, the individual fibers were deposited using the spin coating process on the silicon substrate to form structured fiber films. The prepared fibers and films were characterized by SEM, TEM, XRD, BET, and UV-Vis. The calcination of individual fibers led to the formation of tube-like or full fiber structures in dependence on the doping type of the spinning solution. The full fiber structures with a higher surface area and decreased grain sizes were obtained after doping the precursor solution with Fe3+. On the other hand, doping with Fe3O4 nanoparticles does not have a significant effect on the fibers morphology compared to pure SnO2 tube-like fibers. The resulting morphology of the fibers has a substantial effect on the thickness, roughness, and compactness of the structured final films.