High-purity 2,6-dimethylnaphthalene is prepared by (1) subjecting a dimethylnaphthalene isomer mixture rich in 1,5-dimethylnaphthalene, high boiling point materials, unreacted 1,5-dimethyltetralin, and low boiling point materials, which are produced from a dehydrogenation reaction of 1,5-dimethyltetralin, to separation, using a distillation column; subjecting the dimethylnaphthalene mixture separated by the distillation column to liquid state isomerization in the presence of an isomerization catalyst; (3) a first crystallization (melt crystallization process) by cooling the product of liquid state isomerization with a refrigerant without a solvent to form crystals; and (4) a second crystallization (solution crystallization process) of mixing the crystals of the first crystallization step with a solvent to form crystals.