The synthesis of miktoarm dendritic−linear star copolymers in a tandem “core-in”/“core-out” approach is described. This synthetic approach is enabled by rational design and synthesis of anorthogonal protected compound containing six sites arranged in an alternating fashion for attachment ofdendrimers and atom transfer radical polymerization of linear polymer chains. The judicious choice ofthe dendrimer surface functionality coupled with the properties of the monomer used in the linear chainallows the creation of amphiphilic molecules capable of supramolecular assembly. 1H NMR and SECstudies of the block copolymers confirmed that the targeted polymer structures were achieved with lowpolydispersities and good yields. The nature and the size of the arms and dendrons had a significantinfluence on the hydrodynamic radii (Rh) measured by dynamic light scattering. Some of thesemacromolecules microphase-separated after annealing.