The synthesis of poly (o-phenetidine) (POEA) was performed via chemical oxidative method and doped with dodecylbenzenesulfonic acid. Electrospun fibers of thermoplastic polyurethane (TPU)/poly o-phenetidine (POEA) blends were produced. Parameters such as the distance between collector and needle, as well as the applied voltage and the ratio of POEA content were evaluated. The fiber morphology, chemical structure and thermal analysis of the mats were analyzed. TPU nanofibers showed cylindrical morphology with many beads and the fiber diameter was around 330 nm. With the addition of POEA at a percentage of 30 wt% it was possible to produce uniform fibers without beads with diameters around 400 nm.