The photochemistry of dimethylsulfide (DMS) was examined in the Southern Ocean to assess its impact on the biogeochemical dynamics of DMS in Antarctic waters. Very high DMS photolysis rate constants (0.16--0.23 h-1) were observed in surface waters exposed to full sunlight. DMS photolysis rates increased linearly with added nitrate concentrations, and 35% of the DMS loss in unamended samples was attributed to the photochemistry of ambient nitrate (29 ¿M). Experiments with optical filters showed that the UV-A band of sunlight (320--400 nm) accounted for ~65% of DMS photolysis suggesting that dissolved organic matter was the main photosensitizer for DMS photolysis. During the austral spring, DMS photolysis was the dominant loss mechanism under non-bloom and non-ice cover conditions owing to the high doses and deep penetration of UV radiation in the water column, low observed microbial consumption rates, and high in situ nitrate concentrations.