Abstract. The sea-surface microlayer (SML) is at the uppermost surface of the ocean, linking the hydrosphere with the atmosphere. The presence and enrichment of organic compounds in the SML have been suggested to influence air–sea gas exchange processes as well as the emission of primary organic aerosols. Here, we report on organic matter components collected from an approximately 50 µm thick SML and from the underlying water (ULW),  ∼  20 cm below the SML, in December 2012 during the SOPRAN METEOR 91 cruise to the highly productive, coastal upwelling regime off the coast of Peru. Samples were collected at 37 stations including coastal upwelling sites and off-shore stations with less organic matter and were analyzed for total and dissolved high molecular weight (> 1 kDa) combined carbohydrates (TCCHO, DCCHO), free amino acids (FAA), total and dissolved hydrolyzable amino acids (THAA, DHAA), transparent exopolymer particles (TEP), Coomassie stainable particles (CSPs), total and dissolved organic carbon (TOC, DOC), total and dissolved nitrogen (TN, TDN), as well as bacterial and phytoplankton abundance. Our results showed a close coupling between organic matter concentrations in the water column and in the SML for almost all components except for FAA and DHAA that showed highest enrichment in the SML on average. Accumulation of gel particles (i.e., TEP and CSP) in the SML differed spatially. While CSP abundance in the SML was not related to wind speed, TEP abundance decreased with wind speed, leading to a depletion of TEP in the SML at about 5 m s⁻¹. Our study provides insight to the physical and biological control of organic matter enrichment in the SML, and discusses the potential role of organic matter in the SML for air–sea exchange processes.