Sulfur dioxide (SO2) emissions from ship exhausts pose serious health and environmental concerns. Herein, the SO2 absorption and desorption characteristics of tertiary amines with different functional groups were explored under simulated ship exhaust gas conditions. Tertiary amines with electron‐donating groups had superior absorption performance to those with electron‐withdrawing groups, and highly polar absorbents exhibited enhanced SO2 absorption loading. Dimethylaniline (DMA) showed excellent desorption performance, outperforming other absorbents (amino acids, ionic liquids, and deep eutectic solvents) in terms of cyclic capacity. Thus, tertiary amines, especially DMA, can be potentially used for the prevention of SO2 emissions from ship exhausts and other desulfurization applications.