A method of separating propylene oxide from a mixture (M) comprising propylene oxide and methanol, said method comprising: (i) introducing said mixture (M) into an extractive distillation column; (ii) additionally introducing an extracting solvent into said extractive distillation column; (iii) distilling propylene oxide overhead from said extractive distillation column as top stream; (iv) withdrawing a bottoms stream from said extractive distillation column; (v) compressing the top stream obtained overhead in (iii) by means of at least one compressor to give a compressed vapor.