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The solubility of sodium chloride (NaCl), sodium bromide (NaBr), and sodium carbonate (Na2CO3) was measured in nine ammonium-based deep eutectic solvents (DESs). The aim of the study is to assess the potential use of these DESs as solvents and electrolytes for the separation of sodium metal from its salts. The studied DESs were prepared by combining ammonium salts with various hydrogen-bond donors (HBDs) or metal halides. It was found that the solubility of the sodium salts in DESs increases with temperature in many cases. The maximum solubility of NaCl achieved was 100 w = 80 in N,N-diethylethanolammonium chloride:zinc(II) chloride (molar ratio 1:3) at 90 °C. In addition, the solubility of the sodium salts was modeled successfully using the non-random two liquid (NRTL) model.