Water-soluble coupling reagent were used to graft 4-carboxyphenylboronic acid onto poly(vinyl amine) by generating amide bonds to prepare modified poly(vinyl amine) containing phenylboronic acid functional groups (PVAm-PBA). Subsequently, both of the modified poly(vinyl amine) and Poly(vinyl alcohol) (PVA) were used to treat the regenerated cellulose membrane surface through controllable layer-by-layer self-assembly to improve the mechanical strength. The results showed that the isoelectric point of PVAm-PBA was pH 7.9. When the layer number of the polymer self-assembly film was 30 at pH 9.5, the tensile strength and tensile stretch of the regenerated cellulose membrane improved 53% and 76%, respectively. Hence, the method mentioned in this paper has a potential application value in modifying the mechanical properties of fiber products.