Fine particulate matter samples were collected in an urban ambient fixed site and, outside and inside residencies in Athens greater area, Greece. n-Alkanes, iso/. anteiso-alkanes and polycyclic aromatic hydrocarbons (PAHs) were identified by gas chromatography and mass spectrometry. The values of concentration diagnostic ratios indicated a mixture of vehicular emissions, fuel evaporation, oil residues and environmental tobacco smoke (ETS) in outdoor and indoor samples. Particulate iso/. anteiso-alkanes, specific tracers of ETS, were detected in both non-smoking and smoking households. The indoor-to-outdoor ratios of particulate iso/. anteiso-alkanes and unresolved complex mixture (a tracer of outdoor air pollution) in non-smoking households were comparable to the measured air exchange rate. This suggested that penetration of outdoor air was solely responsible for the detection of tobacco smoke particulate tracers in indoor non-smoking environments. Overall, residential outdoor concentrations accounted for a large fraction (from 25 up to 79%) of indoor aliphatic and polyaromatic hydrocarbons. Open windows/doors and the operation of an air condition unit yielded also in higher indoor concentrations than those measured outdoors. © 2012 Elsevier Ltd.