The invention discloses an extraction and rectification method for separating a mixture of n-hexane and ethyl acetate. A mixture of dimethyl sulfoxide and N,N-dimethyl acetamide is taken as the extractant, a mixture of n-hexane and ethyl acetate enters a extraction and rectification tower with 30 to 60 theoretical plates from the 15th-40th theoretical plate, the extractant enters the tower from the 6th-20th theoretical plate, the n-hexane is discharged from the top of the extraction and rectification tower, the mixture of extractant and ethyl acetate is discharged from the bottom of the extraction and rectification tower and then fed into an extractant recovery tower with 15 to 30 theoretical plates from the 10th-20th plate, ethyl acetate is discharged from the top of the extractant recovery tower, and the extractant is discharged from the bottom of the extractant recovery tower and recovered. The method has the advantages of low energy consumption, high purity, high yield, simple technology, safety, environment-friendliness, and no pollution, and is capable of achieving clean production.