Synthesis of branched peptides are finding increasing interest in modern biomedicine since these could be regarded as new therapeutic agents in the field of vaccine preparation, antimicrobial and antitumor drugs, apart from being used in biomaterials construction. In this context, we have developed a novel and user-friendly platform based on a bromomaleimide moiety to obtain branched peptides which is found to be stable for all SPPS conditions. The bromomaleimide core was conjugated to n-copies of thiol−peptide in-solution to obtain two/four/eight-armed dendrimers. Using ‘n’ number of bromomaleimide analogues, 2n ligands were incorporated at both bromo and ene positions via a thioether bond. This method has the advantage of high conversion in a short time, thus enabling effortless purification and characterization processes. On the other hand, chemoselective ligation plays a paramount role in protein/peptide chemistry since ligating differently functionalized peptides/epitopes to the same molecule at different sites would pave way for new inventions. With this rationale, three different peptides have been incorporated to bromomaleimide core at different positions. The key reactions of the process are the selective stapling of both thiol- and amino-peptides at two different sites of the core. The thiol-peptide replaces the bromide whereas the amino-peptide attacked at the ene-position of the core revealing differential and selective reactivity. Also, a third peptide can be attached via an amide bond at the carboxylic acid end of the core. All reactions are under mild reaction conditions with respect to temperature, pH and solvent compatibility. Thus, we envisage that this platform will find broad application in protein chemistry, multidrug presentation and vaccine preparation.