The following physical properties of the acetic anhydride – acetone – carbon disulfide system have been investigated: congruent compositions, excess volumes, dielectric constants. For the system acetone – carbon disulfide, the excess volumes and the molar polarizations are much greater than those required by the mixture rule. From this we deduced that this system is very non-ideal and might, at a suitable temperature, form two layers; two liquid layers did indeed form at −73 °C, the upper critical solution temperature occurring somewhere between this temperature and 0 °C. We offer it as a general rule that, if the deviation from additivity of molar polarization is large and positive, two layers will form at a sufficiently low temperature, provided that solid phases do not intervene. This deduction becomes almost a certainty if large positive deviations from additivity of molar volume and large positive heats of mixing are also present.