Microplastics are substrates for microbial activity and can influence biomass production. This has potentially important implications at the sea-surface microlayer, the marine boundary layer that controls gas exchange with the atmosphere and where biologically produced organic compounds can accumulate. In the present study, we used large scale mesocosms (filled with 3 m3 of seawater) to simulate future ocean scenarios. We explored microbial organic matter dynamics in the sea-surface microlayer in the presence and absence of microplastic contamination of the underlying water. Our study shows that microplastics increased both biomass production and enrichment of particulate carbohydrates and proteins in the sea-surface microlayer. Importantly, this resulted in a 3% reduction in the concentration of dissolved CO2 in the underlying water. This reduction suggests direct and indirect impacts of microplastic pollution on the marine uptake of CO2, by modifying the biogenic composition of the sea’s boundary layer with the atmosphere.