There is disclosed a process for producing 3-methyltetrahydrofuran substantially free from any of an alcohol and water which comprises adding an organic solvent capable of forming an azeotropic mixture with an alcohol with an alkyl group having 1 to 3 carbon atoms to a mixed liquid containing 3-methyltetrahydrofuran, the alcohol and/or water as the principal components and, as the case may be, another substance, and distilling the resultant mixture of the mixed liquid and said organic solvent. According to the above process, it is made possible to efficiently separate a mixture of 3-methyltetrahydrofuran and an alcohol and/or water which mixture is difficult to separate with conventional distillation process alone, thereby efficiently producing the objective 3-methyltetrahydrofuran substantially free from any of an alcohol and water.