Herein, PEDOT:PSS/PVP nanofibers were produced by electrospinning. The presence of PEDOT:PSS in the nanofibers was confirmed by FT-Raman spectroscopy. The applied voltage-dependent diameter of PEDOT:PSS/PVP nanofibers was observed. Also, sensing behaviors of electrospun PEDOT:PSS/PVP nanofibers were explored by measuring its response upon cyclic exposure to organic vapours such as ethanol, methanol, THF, and acetone at room temperature. When PEDOT:PSS/PVP nanofibers were exposed to each solvent, the protic and aprotic solvents resulted in opposite electrical responses. These findings exhibit that electrospun PEDOT:PSS/PVP nanofibers are the promising candidate for the organic vapour sensing material. (C) 2010 Elsevier B.V. All rights reserved.