Methanol (CH₃OH) is used as solvent in the alcoholysis of polyvinyl alcohol (PVA), so the PVA particles generally contain no less than about 2.0% CH₃OH. How to remove CH₃OH from PVA is a problem worth studying. Aiming at the problem of CH₃OH content reduction in PVA 24-88, the alcoholysis degree and CH₃OH content of PVA after drying were figured out by introducing a trace water in the alcoholysis process. The experimental results demonstrate that the CH₃OH content of PVA products decreases to 0.26% under the addition of 1.0% water. In addition, the effects of water addition on the thermogravimetric behavior and sodium acetate content of alcoholysis PVA in different atmospheres were discussed in detail. When the water addition is 1.0% and 2.0% , the sodium acetate content is only 1.53% and 1.24% , both lower than that of alcoholysis samples. Meanwhile, the results of GC-MS show that the contents of methyl alcohol and methyl acetate in the solvent after alcoholysis increase and decrease with the increase of water addition, respectively. Finally, the relationship between the time of drying process and volatilization of PVA 24-88 without adding water was explored. The results reveal that the percentage of CH₃OH and methyl acetate in the condensation reflux component increases and decreases monotonously with the extension of time, and their respective contents gradually decrease with the extension of drying time. The results are conducive to providing guidance for the practical production problems of PVA.