Concentrations of dissolved and particulate polycyclic aromatic hydrocarbons (PAHs) were determined seasonally in sea surface microlayer (SML) and sub-surface water (SSW) within the Saronicos Gulf, Greece, close to a highly industrialized coastal zone. For the 16 US EPA priority PAHs, the sum of dissolved PAHs (∑dPAHs) concentrations ranged from 40.4 to 237 ng L−1 in SML, 22.8–180 ng L−1 in SSW0.2, whereas the corresponding concentrations in suspended particulate matter (∑pPAHs) were 30.8 to 177 ng L−1 and 36.8–171 ng L−1, respectively. The enrichment factor (EF) for dissolved ∑dPAHs varied from 0.9 to 2.1 with a mean value of 1.5 (n = 10) being statistically significantly greater than unity, whereas for particulate ∑pPAHs, no enrichment of the SML was reported. Enrichment factors of 5–6 ring PAHs were higher near the industrial zone. The possible sources, fate, and toxicity of PAHs are also discussed.