The objective of this study was to identify and quantify the sources of fine particulate aliphatic and polycyclic aromatic hydrocarbons (PAHs) in an urban area in southeastern Europe. A total of 91 urban PM2.5 samples were analyzed by gas chromatography coupled with mass spectrometry for alkanes and PAHs. Exploratory statistical tools were applied to resolve a decreased number of components based on the variation of measurements. Molecular markers and diagnostic ratios were examined to assign retained components to specific sources. The contributions of the sources were estimated by multivariate linear regression. Sources of aliphatic and PAHs hydrocarbons included primary particles from traffic (3.9 ng/m3 for alkanes and 240 pg/m 3 for PAHs), evaporative fugitive (4.0 ng/m3 for alkanes and 93 pg/m3 for PAHs), and unburnt fuels and oil residues (1.1 ng/m3 for alkanes and 230 pg/m3 for PAHs). For the first time, we quantified the contribution of environmental tobacco smoke (ETS), which accounted for 5.2 ng/m3 of alkanes and 128 pg/m3 of PAHs. The findings of this study underlined the persistence of ETS and possible exposures to significant quantities of tobacco residues outdoors. Tobacco smoke is known to induce adverse respiratory and cardiovascular illnesses and increased risk for cancer. © 2012 Springer Science+Business Media New York.