A simple solid-phase synthesis of thioether-linked chiral bicyclic guanidinium oligomers for cell internalization purposes has been developed. The approach is based on a Merrifield-like peptide synthesis on Rinkamide-p-methylbenzhydrylamine resin functionalized with Cys(methoxytrityl). A difunctionalized bicyclic guanidinium synthon, bearing both electrophile (O-mesyl) and protected nucleophile (S-methoxytrityl) group, is repeatedly grafted via a nucleophilic substitution. The sequence requires removal of methoxytrityl, reduction with 1,4-dithiothreitol to cleave any adventitious disulfides, coupling and capping with benzyl bromide. Moreover, Alloc protection of the α-amino group of the initial cysteine, provides a potential handle for cargo attachment after oligomer elongation to the desired internalizing agent and prior to cleaving it from the resin. Finally, a bicyclic guanidinium monomer containing an amino group and a carboxylic acid function has been evaluated as an alternative building block for novel amide-bridged oligomers or peptidomimetics.