In this work, solubility of exo-3,6-epoxy-1,2,3,6-tetrahydrophthalic anhydride (ETA) was measured and discussed in acetone + ethanol, methyl acetate + ethanol, 1,4-dioxane + ethanol, and ethyl acetate + ethanol mixture solvents in a temperature range from 278.15 to 323.15 K by a gravimetric method under 0.1 MPa. Experimental results indicated that solubility increased with temperature increasing and declined with the mass fraction increasing of ethanol in four kinds of mixture solvents. The solvent effect and Hansen solubility parameter were adopted to discuss the solubility behavior of ETA in selected solvents. Modeling correlation solubility data about ETA indicated that the Jouyban-Acree-Apelblat model (J-A-A) was more suitable than the Jouyban-Acree-Van't Hoff model (J-A-V) and Ma and Sun model in mixture solvents. Processing of the dilution crystallization in acetone + ethanol system was chosen to separate and purify ETA on the basis of the solubility and solvent characteristics.