Marine phytoplankton emit volatile organic compounds (VOCs) such as dimethyl sulfide (DMS) and isoprene that influence air quality, cloud dynamics, and planetary albedo. We show that globally (i) marine phytoplankton taxa tend to emit either DMS or isoprene, and (ii) sea-water surface concentration and emission hotspots of DMS and isoprene have opposite latitudinal gradients. We argue that a convergence of antioxidant functions between DMS and isoprene is possible, driven by potential metabolic competition for photosynthetic substrates. Linking phytoplankton emission traits to their latitudinal niches, we hypothesize that natural selection favors DMS emission in cold (polar) waters and isoprene emission in warm (tropical) oceans, and that global warming may expand the geographic range of marine isoprene-emitters. A trade-off between DMS and isoprene at metabolic, organismal, and geographic levels may have important consequences for future marine biosphere-atmosphere interactions.