In this work, the performance of inorganic salt sodium chloride and ionic liquid (molten salt) ECOENG212 as salting-out media for the separation of nicotine from its aqueous solutions was examined. In this respect, liquid–liquid equilibria of the ternary solutions nicotine + water + NaCl and nicotine + water + ECOENG212 were determined at ambient pressure, 0.1 MPa, and humidity at three temperatures. The related phase diagrams were constructed by means of both cloud points and chemical analysis of phases in equilibrium (tie-line data). The latter were used to calculate two important separation parameters: partition coefficients of nicotine and separation factors. The effects of the initial compositions of the solutions and of the temperature on the phase behavior and partition coefficients were analyzed and discussed. The results obtained, particularly in the case of sodium chloride as a salt, clearly showed that both investigated salts provided good salting-out media for the efficient and sustainable separation of nicotine from solutions with water.