This invention provides smoking compositions which contain a dioxane diester compound as a flavorant additive.In one of its embodiments, this invention provides tobacco compositions which contain a dioxane diester flavorant additive such as 2,5-bis(3-methylvaleryloxy)-1,4-dioxane: ##STR1## Under cigarette smoking conditions the above illustrated dioxane diester pyrolyzes into 3-methylvaleric acid and other products which enhance the flavor of the mainstream smoke and the aroma of sidestream smoke.