Dimethyl carbonate is obtained pure, from its solutions in methanol, by extractive distillation carried out with a temperature of from 60.degree. C. at the top to 250.degree. C. at the bottom of the column and employing, as the extractant, an aprotic organic liquid which is substantially inert toward dimethyl carbonate, boils at above 100.degree. C. at standard pressure, is miscible with dimethyl carbonate in all proportions and has a dielectric constant .epsilon. of from 4 to 90 and a dipole moment .mu. of from 1.5 to 5 Debye.