This paper reports the alkaline hydrolysis of poly(methyl glutamate), poly (benzyl glutamate) and copoly(methyl glutamate-benzyl glutamate-glutamic acid) for de-esterification. The results showed that in this process of alkaline hydrolysis the demethylation of poly(methyl glutamate) was faster, but debenzylation of poly(benzyl glutamate) was hardly processed. An increase in the methyl glutamate content of starting copolymers, in the alkaline concentration and the time of alkaline hydrolysis, and a decrease in the film thickness, would lead to a raise in the degree of alkaline hydrolysis, that is, an increase of the glutamic acid segment content in product of alkaline hydrolysis.