Methyl acrylate has a wide range of uses, but the production process usually produces aqueous by-products. In this study, four commonly used alcohols (1-pentanol, 1-hexanol, 1-heptanol, and 1-octanol) were selected as extractants to explore the liquid–liquid extraction behavior of water + methyl acrylate + extractants. Through the analysis of partition coefficient (D) and separation coefficient (S), it is found that the data of all systems are greater than 1, indicating that all four alkyl alcohols can well separate methyl acrylate from aqueous solution, and 1-octanol is the best. In addition, the consistency between the binary interaction parameters of regression and tie-line data was tested using Matlab tools, proving that the obtained parameters have good consistency.