An organic salt (FeAOT) is synthesized by the reaction of sodium 1,4-bis(2-ethylhexyl)sulfosuccinate (AOT) and ferric chloride. It is fabricated into fibers by manual drawing and electrospinning. Long polypyrrole (PPy) fibers are obtained for the first time by a vapor deposition reaction of pyrrole on the FeAOT fibers, and this technique is extended to the synthesis of PPy composite fibers with multiwalled carbon nanotubes (PPy-MWCNT fibers). The PPy and PPy-MWCNT fibers have a nanoporous morphology, a conductivity of 10-15 S cm(-1), and a tensile strength of 12-43 MPa. The electrochemistry and current-voltage characteristics of the PPy fibers are also studied. (c) 2006 Wiley Periodicals, Inc.