The synthesis and structural characterization of the first organometallic-polypeptide block copolymers, poly(ferrocenyldimethylsilane)-b-poly-(γ-benzyl-L-glutamate) was performed. The deprotection of the material to form the water-soluble organometallic-polypeptide block copolymers, PFS-b-poly(L-glutamic acid) (PFS-b-PGA) was also discussed. The macroinitiator PFS-NH2 was used for the ROP of γ-benzyl-L-glutamate NCA to obtain the organometallic-peptide block copolymers. The 1H NMR of the purified PFS-NH2 in C6D6 showed a signal at 2.47 ppm, which corresponded to the methylene protons adjacent to the terminal amino group.