Taking into account their atmospheric characteristics, generally under photochemical conditions, forested areas of Mediterranean countries constitute an appropriate environment to investigate the secondary organic aerosols. The objective of this study was to study in situ the aerosol composition, particularly in the photo-oxidation products of biogenic volatile organic compounds, taking into consideration anthropogenic inputs, and to explain how these compounds appear in the aerosols. Atmospheric particulate matter was collected at two sites: an Abies boressi forest in central Greece and at Giesta, a coastal-rural site in the centre of Portugal. The collected aerosol was extracted with solvents and characterised by gas chromatography and mass spectrometry. The detected secondary organics include alkene derivatives, oxo-, di- and monocarboxylic acids, oxy-aromatics, aza and thia arenes, and many terpene photo-oxidation products. This in situ experiment allowed confirming the presence of secondary constituents, which have been studied almost exclusively under simulated laboratory conditions. Some reaction pathways leading to the formation of compounds in the particulate phase from precursors are presented.