Studying the freezing of saltwater on a molecular level is of fundamental importance for improving freeze desalination techniques. Here, we investigate the freezing process of NaCl solutions using a combination of x-ray diffraction and molecular dynamics simulations (MD) for different salt-water concentrations, ranging from seawater conditions to saturation. A linear superposition model reproduces well the brine rejection due to hexagonal ice Ih formation and allows us to quantify the fraction of ice and brine. Furthermore, upon cooling at T = 233 K we observe the formation of NaCl×2H2O hydrates (hydrohalites), which coexist with ice Ih. MD simulations are utilized to model the formation of NaCl crystallites. From the simulations we estimate that the salinity of the newly produced ice is 0.5% mass percent (m/m) due to ion inclusions, which is within the salinity limits of fresh water. In addition, we show the effect of ions on the local ice structure using the tetrahedrality parameter and follow the crystalite formation by using the ion coordination parameter and cluster analysis. Fig.1 A schematic phase diagram of NaCl aqueous solution.Above the melting point and in low concentration of NaCl the solution is in liquid phase. At higher concentrations, saturation leads to NaCl crystal or NaCl×2H2O hydrates formation (shown on the right). Upon decreasing the temperature below the melting point, ice is formed pushing out the salt, in a process called brine rejection. When decreasing further the temperature below 251.9 K, ice and NaCl×2H2O crystals coexist. These authors contributed equally to this work.