In the previous study, we successfully prepared a chitin nanofiber film by regeneration from a chitin ion gel with an ionic liquid using methanol. In this study, we performed surface-initiated graft polymerization of gamma-benzyl l-glutamate N-carboxyanhydride (BLG-NCA) from amino groups on a partially deacetylated chitin nanofiber (PDA-CNF) film. First, the chitin nanofiber film was immersed in 40 % NaOH aq. at 80 A degrees C for 7 h for partial deacetylation. Then, the PDA-CNF film was immersed in a solution of BLG-NCA in ethyl acetate at 0 A degrees C for 24 h for graft polymerization from amino groups on nanofibers to give a chitin nanofiber-graft-poly(gamma-benzyl l-glutamate) (CNF-g-PBLG) film. The analytical results of the film indicated that graft polymerization of BLG-NCA occur on surface of nanofibers. Furthermore, the film was treated with 1.0 mol/L NaOH aq. to convert PBLG on nanofibers into poly(gamma-l-glutamic acid sodium salt) (PLGA). Then, condensation of the resulting carboxylates with amino groups at the terminal ends of PLGAs or the remaining amino groups on nanofibers was performed using the condensing agent to produce a CNF-g-PLGA network film. The resulting film showed the good mechanical properties with high flexibility, which has potentials as promising materials for practical applications.