SAN/BMIPF6 nanofibers were fabricated by an electrospinning process and used as chemiresistors for sensing alcohol vapours. A hydrophobic and air-stable ionic liquid, BMIPF6, was used to impart electrical conductivity to insulating SAN nanofibers. The effects of BMIPF6 addition on the morphology of the nanofibers were explained in terms of surface tension, viscosity and conductivity. After exposing the SAN/BMIPF6 nanofibers collected on an interdigitated electrode to alcohol vapours (ethanol, 1-propanol and 1-butanol), the resistance of the nanofibers decreased due to adsorption of alcohol molecules. The electrospun SAN/BMIPF6 nanofibers sensor exhibited good sensitivity and reproducibility.