Sea ice plays a dynamic role in the air‐sea exchange of CO2. In addition to abiotic inorganic carbon fluxes, an active microbial community produces and remineralizes organic carbon, which can accumulate in sea ice brines as dissolved organic matter (DOM). In this study, the characteristics of DOM fluorescence in Antarctic sea ice brines from the western Weddell Sea were investigated. Two humic‐like components were identified, which were identical to those previously found to accumulate in the deep ocean and represent refractory material. Three amino‐acid‐like signals were found, one of which was unique to the brines and another that was spectrally very similar to tryptophan and found both in seawater and in brine samples. The tryptophan‐like fluorescence in the brines exhibited intensities higher than could be explained by conservative behavior during the freezing of seawater. Its fluorescence was correlated with the accumulation of nitrogen‐rich DOM to concentrations up to 900 mmol L−1 as dissolved organic carbon (DOC) and, thus, potentially represented proteins released by ice organisms. A second, nitrogen‐poor DOM fraction also accumulated in the brines to concentrations up to 200 mmol L−1 but was not correlated with any of the fluorescence signals identified. Because of the high C:N ratio and lack of fluorescence, this material is thought to represent extracellular polymeric substances, which consist primarily of polysaccharides. The clear grouping of the DOM pool into either proteinaceous or carbohydrate‐dominated material indicates that the production and accumulation of these two subpools of DOM in sea ice brines is, to some extent, decoupled.