An analytical method, based on separation with gas chromatography (GC) and detection with optical fiber (OF), was used for the separation, detection and quantification of benzene, toluene, ethylbenzene, p-xylene, m-xylene and o-xylene. The use of OF as a detector is based on the variations of the reflected optical power detected when the aromatic compounds eluted from the GC column are sorbed in a thin polymeric film on a single-mode OF. General figures of merit, such as the analytical time, analytical error and analytical performance of GC-OF were similar to those of the classical analytical methods, such as a gas chromatography-flame ionization detector (GC-FID). However, the developed GC-OF method constitutes a much less expensive alternative for the speciation of aromatic hydrocarbons compounds, with high accuracy, and being most suitable for actual monitoring work on confined environments.