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The invention relates to a method for separating dimethyl carbonate methanol azeotrope through melt crystallization and application thereof. The method specifically comprises the following steps: introducing a dimethyl carbonate methanol azeotrope with the dimethyl carbonate content of 25-35% into a melt crystallization device, separating out dimethyl carbonate in a crystal form through cooling, then partially melting dimethyl carbonate crystals through heating sweating, removing impurities contained in the crystallization process, further purifying dimethyl carbonate, and finally obtaining ahigh-purity dimethyl carbonate product and a low-concentration crystallization mother solution. The crystallization temperature of dimethyl carbonate in a self-azeotropic system is -20 to -40 DEG C, and the operation equilibrium temperature of a crystallization section is -50 to -60 DEG C, the purity of the dimethyl carbonate product is 99.9%-99.999%, and the concentration of the crystallization mother solution is 5%-15%. The method can be used for separation and purification of dimethyl carbonate methanol azeotropic composition in the process of producing dimethyl carbonate by a synthesis method or producing dimethyl carbonate as a byproduct in the coal-to-ethylene glycol process, and has the advantages of low energy consumption, high product purity and the like compared with traditionalseparation modes such as pressurized distillation, extractive distillation or azeotropic distillation.