To provide a method of stably separating cyclohexyl nitrate by preventing cyclohexyl nitrate from thermally decomposing in separating cyclohexyl nitrate from an organic substance containing cyclohexyl nitrate by steam distillation.

The method of separating cyclohexyl nitrate from an organic mixture containing cyclohexyl nitrate by steam distillation comprises carrying out the steam distillation in a manner that the liquid temperature of the bottom of a distillation column 1 is set at not higher than 182C and the concentration of the cyclohexhyl nitrate in a bottom product to be drawn from the bottom of the column comes to not more than 45 mass% by the cyclohexyl nitrate concentration in an organic phase separated from an aqueous phase.