Boundary layers between different environmental compartments represent critical interfaces for biological, chemical and physical processes. The sea-surface microlayer (uppermost 1-1000 microm layer) forms the boundary layer interface between the atmosphere and ocean. Environmental processes are controlled by the SML, and it is known to play a key role in the global distribution of anthropogenic pollutants. Due to its unique chemical composition, the upper organic film of the SML represents both a sink and a source for a range of pollutants including chlorinated hydrocarbons, organotin compounds, petroleum hydrocarbons, polycyclic aromatic hydrocarbons (PAH) and heavy metals. These pollutants can be enriched in the SML by up to 500 times relative to concentrations occurring in the underlying bulk water column. The SML is also a unique ecosystem, serving as an important habitat for fish eggs and larvae. Concentration ranges and enrichment factors of pollutants in the SML in different areas of the world's oceans have been critically reviewed, together with available toxicity data for marine biota found within the SML. Overall, the SML is highly contaminated in many urban and industrialized areas of the world, resulting in severe ecotoxicological impacts. Such impacts may lead to drastic effects on the marine food web and to fishery recruitment in coastal waters. Studies of the toxicity of fish eggs and larvae exposed to the SML contaminants have shown that the SML in polluted areas leads to significantly higher rates of mortality and abnormality of fish embryos and larvae.