N-nitrosamines are potentially hazardous pollutants, classified as probable carcinogenic and mutagenic by the U.S. Environmental Protection Agency (EPA). In this paper, the presence of these pollutants was studied in air samples taken at different locations of Tarragona (urban and harbour). As a result, a reliable method has been developed for determining N-nitrosamines and nicotine based on pressurised liquid extraction (PLE) and gas chromatography-(chemical ionisation) ion trap tandem mass spectrometry (GC-(CI)MS/MS). The chromatographic analysis enables the determination of these compounds in less than 13min with total separation and good resolution between the compounds. Recovery values were higher than 80% for most of the compounds and the repeatability of the method was under 18% (5ngm−3, %RSD, n=4). MDLs were between 0.1ngm−3 (NMor and NPip) and 2ngm−3 (NMEA). NMor, NPyr, NPip and nicotine were the most frequent compounds in urban and harbour samples at concentration levels between 0.3ngm−3 (NPyr) and 12.5ngm−3 (nicotine) and between 0.13ngm−3 (NPyr) and 3.8ngm−3 (nicotine), respectively.