An analytical method for the determination of 15 Volatile Organic Compounds (VOC): benzene, n-heptane, toluene, n-octane, chlorobenzene, ethylbenzene, m-xylene, o-xylene, p-xylene, isopropylbenzene, n-propylbenzene, n-decane, 1,4-dichlorobenzene, 1,3-dichlorobenzene and 1,2-dichlorobenzene, by thermal desorption coupled with gas chromatography (GC) was proposed. The flame ionisation detector (FID) and mass spectrometry (MS) detector were used. The variables that have an influence on the desorption process (time, inert gas flow and temperature) were studied, obtaining detection limit ranges from 15 to 120 pg (GC-FID), 3.8 to 32 pg (GC-MS, SIM mode) and 15 to 300 pg (GC-MS, SCAN mode). In order to detect possible VOC urban sources, samples were taken from 6 points in A Coruña (N.W. Spain) to analyse. Sampling time and flow rate were 30 minutes and 50 mL/min respectively. VOC profile and their total concentrations can be considered as typical of an urban area. Other samples were also obtained from a nearly rural zone to determine the influence of these VOC sources.