AbstractDissolved organic matter (DOM) plays a key role in global biogeochemical cycles and experiences changes in molecular composition as it undergoes processing. In the semi-closed basins of the oligotrophic Mediterranean Sea, these gradual molecular modifications can be observed in close proximity. In order to extend the spatial resolution of information on DOM molecular composition available from ultrahigh resolution mass spectrometry in this area, we relate this data to optical (fluorescence and absorption spectroscopy) measurements. Covariance between molecular formulae signal intensities and carbon-specific fluorescence intensities was examined by means of Spearman’s rank correlations. Fifty two per cent of the assigned molecular formulae were associated with at least one optical parameter, accounting for 70% of the total mass spectrum signal intensity. Furthermore, we obtained significant multiple linear regressions between optical and intensity-weighted molecular indices. The resulting regression equations were used to estimate molecular parameters such as the double bond equivalent, degradation state and occurrence of unsaturated aliphatic compounds from optical measurements. The statistical linkages between DOM molecular and optical properties illustrate that the simple, rapid and cost-efficient optical spectroscopic measurements provide valuable proxy information on the molecular composition of open ocean marine DOM.