Electrospun mats have been prepared by blending emeraldine base (EB) or DBSA-doped polyaniline (PANI.DBSA) with poly(vinylidene fluoride) (PVDF). In order to understand the effect of doped and undoped PANI on the structure and properties of PVDF/PANI mats, the electrical, conductivity, doping degree and morphology of the electrospun mats were investigated. The effect of PANI.DBSA and EB content on the properties of PVDF solution and fibers morphology was investigated. The addition of either doped or undoped PANI increases the viscosity of the PVDF solution, but the ionic conductivity was. changed significantly by adding doped PANI. The PVDF/EB fibers manifested a core-sheath structure, while PANI agglomerates were homogeneously distributed in the PVDF/PANI.DBSA. This morphology associated to the high porosity of mat resulted in insulating mats, even when 23 wt% of PANI salt was used and high doping levels were achieved. The PVDF/EB mats obtained from electrospinning displayed a considerable doping level, indicating that the electrical field could induce the protonation of PANI. (C) 2015 Elsevier B.V. All rights reserved.