The trioxane-water system exhibits a positive azeotrope. Extraction is used to separate trioxane from the solution and the solvent selection is critical to the extraction. The main parameters influencing upon solvent selection for the extraction such as solubility, selectivity, loss and recovery of solvent are investigated in the present paper. The candidate solvents for the separation of trioxane and water by extraction are comprehensive evaluated. Chlorobenzene is the most suitable separation solvent.