The separation of the extractant from the diluent solution is a crucial step in the development of clean technologies. Solid–liquid equilibrium (SLE) is used to develop an energy-saving recycling process for extracting solvent. The SLE of the binary systems {Alamine 336+decane}, {Alamine 336+dodecane}, and {Alamine 336+1-dodecanol}, which were used as selective solvents, diluents, and modifiers in the extraction of molybdenum (Mo), was determined at atmospheric pressure by the visual method. The experimental SLE data have been correlated by the Non-Random Two-Liquid (NRTL) model. In addition, we determined the excess molar volume (V E ) and deviations in molar refractivity (ΔR) for the same binary mixtures at 298.15K and correlated them with the Redlich–Kister equation.