A complete phase diagram was determined for the system: water, butanol, propanol, and tetramethyldioctyldisiloxane (TDDS) using refractive index and gas chromatography. The solubility limits were established by quantitative analysis and compared to the refractive index of known single-phase mixtures. The system contained three two-phase regions and one three-phase region, which separated from one large continuous single phase. The system exhibited a preferential phase stability, which inversely changed with the increase in polarity of the solution. Once a ratio of 3-1 water-propanol was obtained, the phase separation shifted from TDDS to water. The content of the amphophilic components influenced the solubility of TDDS and is reflected in the phase equilibria.