Among the introduced polymers, polyaniline (PANI) has special interest due to the high electrical conductivity. In this study, electrospun nanofiber mats composed of PANI and poly(vinyl acetate) (PVAc) are introduced. Typically, PANI and PVAc were individually dissolved in tetrahydrofuran and dimethylformamide, respectively. The polymer solutions were mixed in different ratios. The final solutions were electrospun using silicon substrate as a collector, so electrospun nanofiber mats containing different PANI contents (2, 3.5, 4.5 and 5 wt%) were obtained in the form of well attached thin layer on the silicon substrates. Electrical properties study indicated that the synthesized nanofibers behave as organic semiconductors. Leakage current study indicated that Schottky emission is the dominant mechanism through both of the negative and positive bias regions. In the positive bias, the conductivity was found to be linearly dependent on the PANI content. Moreover, the electron paramagnetic resonance (ESR) measurement indicated the presence of polarons, the g-factor value was estimate to be 2.0033. Overall, the introduced electrospun nanofiber mats might be utilized as effective organic semiconducting materials.