A method of desalinating an aqueous composition includes forming a hetero-azeotrope mixture by combining the aqueous composition with an entrainer, the aqueous composition including at least one salt, and subjecting the hetero-azeotrope mixture to distillation at a distillation temperature of less than the boiling temperature of the aqueous composition for an operating distillation pressure, resulting in separating the hetero-azeotrope mixture into a distillation bottoms liquid and a multi-phase condensate. The method includes recovering the multi-phase condensate having an entrainer-rich phase and an aqueous phase, the aqueous phase comprising desalinated water, and removing a portion of the aqueous phase from the multi-phase condensate to recover the desalinated water. Systems for conducting the method of desalinating an aqueous stream are also disclosed.