Volatile organic compounds (VOCs) sensors are the imperative technology of modern life for environmental monitoring to detect any harmful elements and to prevent lethal exposure. The sensing material is a fibrous film consisting of poly(3-hexylthiophene)(P3HT)/poly(methyl methacrylate)(PMMA) blend, and it is fabricated on a glass substrate. The P3HT/PMMA fibrous film is made by electrospinning process and shows high specific surface for solvent vapor harvesting. The P3HT/PMMA fibrous films are thus easily designed according to the extinction changes of VOCs. The P3HT/PMMA fibrous film exhibits the detection capability for VOCs. It satisfies the detection limit of acetone, toluene and o-xylene at 500 ppm. The cost of the P3HT/PMMA fibrous film is acceptable to the market in contrast to the commercial sensors toward VOCs. (C) 2017 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved.