The electrochemical behavior of electrospun polypyrrole (PPy)/sulfonated-poly(styrene-ethylene-butylenes-styrene) (S-SEBS) composite nanofibers was investigated, compared to PPy/poly(styrene-ethylene-butylenes-styrene) (SEBS) fibers prepared by a casting method. The electrospun PPy/S-SEBS (E-PSS) fibers were about 300nm in average diameter, while PPy/SEBS composite (C-PS) prepared by a casting method showed the granular macroporous structure. The effect by both electrospinning and sulfonation results in higher electrochemical capacity due to the increase of doping level, high electrical conductivity, low interfacial resistance, and high reversibility by easy intercalation of Li ion. In addition, sulfonated SEBS induces higher elongation force to jet in the processing of electrospinning due to the role of dopant.