Abstract: Polypyrrole (PPy) was synthesized by chemical oxidation methods in the presence of toluene sulfonate (TSNa), dodecyl sulfonic acid sodium salt (DSNa), dodecyl-benzene sulfonic acid sodium salt (DBSNa) and di-(2-ethylhexyl) sulfosuccinate sodium salt (DEHS), and then PPy was mixed with polyvinyl alcohol (PVA). PVA-PPy composite nano fibers were prepared via electrospinning. The microstructure, thermal stability and conductivity properties were investigated using SEM, TGA and four-probe tester. The results show that dopants, PPy preparation technology and polymer additives have a great influence on the electrical properties of PPy. The conductivity of nanofibers is much higher than the obtained PVA-PPy films and PPy powders with the same dopant. The conductivity of DEHS doped PVA-PPyPVA-PPy nanofibers is highest among all nanofibers, which reaches to 26.64 S/cm.