Separation of naphthalene from naphthalene and 2-methylnaphthalene mixture has been studied by layered melt and solution crystallization using ethylalcohol. Purity and yield of naphthalene depended mainly on the cooling rate: The effective distribution coefficient (Keff) as the degree of impurity removal was observed to decrease with the decreasing in cooling rate. Purity of naphthalene can be enhanced to 5~7% by melt crystallization using 90% naphthalene and the purity of naphthalene can be obtained to be 99% up by solution crystallization.