The invention belongs to the technical field of chemical production and relates to a method for preparing electronic dimethyl carbonate by coupling rectification with crystallization. The method for preparing electronic dimethyl carbonate by coupling rectification with crystallization provided by the invention comprises the following steps: reactive distillation, namely taking methyl alcohol and ethylene carbonate as raw materials, performing transesterification in a reactive distillation column under the existence of catalyst, acquiring an ethylene glycol solution at the bottom of the reactive distillation column and acquiring the dimethyl carbonate in mass fraction of 98%-99.5% at the top of the reactive distillation column; and falling film crystallization, namely conveying the dimethyl carbonate acquired from the top of the reactive distillation column into a falling film crystallizer, crystallizing in the manner of gradually cooling, stopping till cooling to -5 DEG C to 2 DEG C and then acquiring the dimethyl carbonate in mass fraction of 99.99% in the manner of gradually warming, sweating and fully melting. The method has the advantages of simple operation, easiness in control, high purity and high yield of prepared products, stable product quality, low cost and low energy consumption.