Size-segregated samples of urban particulate matter (<0.95, 0.95–1.5, 1.5–3.0, 3.0–7.5, >7.5 μm) were collected in Thessaloniki, northern Greece, during winter and summer of 2007–2008, in order to study the size distribution of organic compounds such as polycyclic aromatic hydrocarbons (PAHs), aliphatic hydrocarbons (AHs) including n-alkanes and the isoprenoids pristane and phytane, organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs). All organic compounds were accumulated in the particle size fraction <0.95 μm particularly in the cold season. Particulate matter displayed a bimodal normalized distribution in both seasons with a stable coarse mode located at 3.0–7.5 μm and a fine mode shifting from 0.95–1.5 μm in winter to <0.95 μm in summer. Unimodal normalized distributions, predominant at 0.95–1.5 μm size range, were found for most organic compounds in both seasons, suggesting gas-to-particle transformation after emission. A second minor mode at larger particles (3.0–7.5 μm) was observed for C 19 and certain OCPs suggesting redistribution due to volatilization and condensation.