An analytical methodology based on an optical fibre detector coupled to gas chromatograph has been developed for the speciation of some volatile alcoholic compounds. This methodology combines the separation capability of gas chromatography with an optical fibre detector made of an optical fibre sensitized with a thin polymeric film of poly[methyl(3,3,3-trifluoropropyl)siloxane] (PMTFPS). The response of the detector has been characterized at 650 nm for nine different alcohols (allyl alcohol, n-propyl alcohol, sec-butyl alcohol, isobutyl alcohol, n-butyl alcohol, isoamyl alcohol, methyl isobutyl carbinol, cyclohexanol and diacetone alcohol). An alternative method based on gas chromatography-flame ionization detector (GC-FID) was also used in order to evaluated the performance and compare the analytical results with the proposed method. The time of analysis, the analytical error and the analytical performance were similar for both methods. However, the analytical apparatus based on the GC-OF detector is much less expensive than the GC-FID and show high accuracy and suitability for actual monitoring on indoor atmospheres.