Doped polyaniline (PANI) was obtained by the polymerization of aniline, using chemical oxidative polymerization in the presence of ammonium peroxydisulfate [(NH4)2S2O8]. The doped PANI was dedoped by ammonia solution. The electrospinning method was applied to solutions involving PANI–PVA, PANI–PVA–AgNO3, where PV A=poly(vinyl alcohol) and PANI=polyaniline. Micro to nanofibers were obtained in the cases of PANI–PVA and PANI–PVA–AgNO3. The SEM technique was used to investigate the morphology of the accumulated fibers or particles on the Al surface collector. Thermal analysis performed on PANI–PVA composite fibers indicated an endothermic peak at 280–420 °C, accompanied by 90% weight loss. The presence of Ag in the case of Ag containing composite fibers was confirmed by EDAX.