Synthetic polypeptides are intensively studied for drug delivery systems and their self-assembly behaviors are directly influenced by both copolymer architecture and the secondary conformations.It is reported that the secondary structure of polypeptides can be adjusted by different side groups (e.g.,ionic charge,chain length,and steric hindrance) [1].The glycosylated poly(L-cysteine) presented a helical structure and a redox-triggered helix-to-coil transition [2].Thermosensitive OEGylated poly(Lcysteine) assumed from mixed conformations to random coil with increasing OEG chain length [3].In our previous work,photo-responsive poly(S-(o-nitrobenzyl)-L-cysteine) (PNBC) and PNBC-b-PEO was developed,which exhibited a stable conformation before and after UV irradiation [4].Herein,we can easily manipulate the side groups of PNBC by utilizing photochemistry and thiol-ene chemistry,and both the side groups and the grafting ratio are able to direct the self-assembled nanostruetures (Fig.1).