This paper reports the synthesis and characterization of a novel class of dendronized polymers which are based on styrene functionalized dendritic L-lysine macromonomers. Free radical polymerization of zeroth and first generation macromonomers afforded dendronized polymers with number-average degrees of polymerization (DP) between 50 and 240, corresponding to number-average molecular weights between 50 × 103 and 240 × 103 g/mol. In contrast, only short oligomers (DP = 5-15) were obtained on polymerization of the second generation dendritic L-lysine macromonomers. Molecularly resolved ATM images allowed first insight into the structure of these peptide dendronized polymers. Depending on the degree of polymerization, either rods, short rods, or globular structures were found. © 2005 American Chemical Society.