Poly-L-lysine (PLL) grafted ordered mesoporous material was prepared by a combination of NCA polymerization and click chemistry. Large pore SBA-15 with a mesopore diameter of ∼12 nm was synthesized using a previously reported method. The surface of this SBA-15 material was modified with azidopropyl groups. This “clickable” SBA-15 was then reacted with an alkyne terminated poly-L-lysine synthesized by the ring-opening polymerization of ε-cbz-L-lysine NCA with N-TMS propargylamine as the initiator. This procedure allows grafting of a uniform polymer film with a high polymer loading. No appreciable pore blocking was observed upon grafting of PLL. No change in the periodic structure of the SBA-15 was observed throughout the grafting process. The SBA-15 PLL conjugate was characterized using ¹³C and ²⁹Si NMR, XRD, FT-IR, N₂ adsorption–desorption and thermogravimetry. The results indicate that polypeptides can be easily grafted onto various ordered mesoporous materials by this “grafting to” methodology with accessible pores and high loadings of the polypeptide.