The nature and kinetics of phase separation processes of solutions of cellulose acetate (degree of substitution, 2.5) in mixtures of dioxane and water are studied by differential scanning calorimetry (DSC). The thermograms on heating show small endothermic effects, detectable only after prolonged aging below the phase separation temperature. Experiments in two regions of the ternary diagram are of interest for the description of the formation mechanism of asymmetric membranes viz., (1) at high polymer and high concentrations and low concentrations of nonsolvent (gelation); (2) at lower polymer concentrations of nonsolvent (liquid-liquid separation followed by gelation). Endothermic effects after prolonged aging are found at high polymer concentrations (40%). These results demonstrate that gelation is very slow in these systems. At lower concentrations of polymer and high concentrations of nonsolvent (up to 40%) a more rapid type of phase separation can be observed visually on cooling. The temperature where turbidity sets in (the cloud point) is independent of the rate of cooling. In DSC experiments no exothermic effect is found on cooling. Again, after aging an endothermic effect is present. The endothermic peak, which is situated below the cloud point, is probably a result of melting of the gelled concentrated phase.