Disclosed is a process for purifying propylene oxide. A stream S0 containing propylene oxide, acetonitrile, water, and an organic compound containing one or more of acetone and propionaldehyde is provided. Propylene oxide is separated from S0 by subjecting S0 to distillation in a first distillation unit, obtaining a gaseous top stream S1c enriched in propylene oxide, a liquid bottom stream S1a enriched in acetonitrile and water, and a side stream S1b containing propylene oxide and enriched in the carbonyl compound; reacting the carbonyl compound in S1b with an organic compound containing an amino group to obtain a reaction product; separating propylene oxide from the reaction product in a second distillation unit, obtaining a gaseous top stream S3a enriched in propylene oxide and a liquid bottoms stream S3b enriched in the reaction product; and introducing stream S3a into the first distillation unit.