Abstract: Disclosed are scaffolded maleimide clusters, methods of making said clusters and use of said clusters as templates for multivalent peptide assembly. Multiple maleimide functionalities were introduced onto a scaffold molecule by the reaction of a core-centered polyamines with methoxycarbonylmaleimide or with activated esters of maleimide-containing compounds. The scaffolded maleimides allow rapid, highly chemoselective, and high-yield ligation with thiolcontaining peptides under virtually neutral conditions at room temperature. The disclosed mild and highly efficient ligation method is extremely valuable for synthesizing large and complex multivalent peptides that may not be easily obtained by conventional ligation methods. These novel scaffolded maleimide clusters allow a highly chemoselective ligation with a thiolcontaining peptide under virtually neutral conditions, providing a new and efficient approach for multivalent peptide assembly.