In summary, these results contributed for the first time to verify that even the “reduced version” of the amphiphilic dendron C22G1, that is the single-tail, small DAPMA-based C14G0 and C16G0 amphiphiles, are able to form very stable spherical micelles even when electrostatically bound to heparin, and that the presence of the polyanion induces the adoption of a highly regular, nanoscale hierarchical structure.