Biogenic volatile organic compounds (BVOCs) affect atmospheric chemistry, climate and regional air quality in terrestrial and marine atmospheres. Although isoprene is a major BVOC produced in vascular plants, and marine phototrophs release dimethyl sulfide (DMS), lakes have been widely ignored for their production. Here we demonstrate that oligotrophic Lake Constance, a model for north temperate deep lakes, emits both volatiles to the atmosphere. Depth profiles indicated that highest concentrations of isoprene and DMS were associated with the chlorophyll maximum, suggesting that their production is closely linked to phototrophic processes. Significant correlations of the concentration patterns with taxon-specific fluorescence data, and measurements from algal cultures confirmed the phototrophic production of isoprene and DMS. Diurnal fluctuations in lake isoprene suggested an unrecognised physiological role in environmental acclimation similar to the antioxidant function of isoprene that has been suggested for marine biota. Flux estimations demonstrated that lakes are a currently undocumented source of DMS and isoprene to the atmosphere. Lakes may be of increasing importance for their contribution of isoprene and DMS to the atmosphere in the arctic zone where lake area coverage is high but terrestrial sources of BVOCs are small.