Diblock copolymers consisting of poly(L-phenyl alanine) and poly(benzyl-L-glutamate) or poly(CBZ-L-lysine), respectively, were synthesized via sequential NCA polymerization. After deprotection, subsequent partial glycosylation of the glutamic acid and lysine units with galactosamine hydrochloride or lactobionic acid yielded amphiphilic block copolypeptides. Moreover, a triblock copolymer poly(L-phenyl alanineb-L-benzyl glutamate-b-propargylglycine) was obtained and glycosylated by 'click' chemistry. Glycosylated block copolypeptides showed improved water solubility and circular dichroism (CD) confirmed the pH dependence of the helix-coil transition. The block copolypeptides were found to be efficient stabilizers in the emulsion polymerization of styrene offering a facile method for the synthesis of polystyrene nanoparticles in the range of 100-140 nm depending on the block copolymer composition and emulsion concentration. This establishes an example of functional polymer additives fully based on renewable building blocks in nanomaterial synthesis.This journal is