After the synthesis of these two amphiphilic dendrons was carried out by peptide chemistry and protecting group methodologies, we first experimentally determined both their overall dimensions (by DLS), and self-assembly thermodynamics—via isothermal titration calorimetry (ITC). ITC is a straightforward, non-invasive, and highly-sensitive titration-based method that provides a complete and accurate thermodynamic description of different association processes (e.g., self-assembling and binding, just to name a few) in complex systems [39]. In line with the in silico results, for L-G2, DLS data confirmed the formation of spherical nanomicelles with average Dm = 6.7 ± 0.2 nm, and a positive surface charge, quantified by the zeta-potential value (ζ) of +29.6 ± 2.3 mV. Also, for L-G1, DLS supported the modeling view of its self-assembling in non-spherical, larger structures. In fact, the relevant data, fitted using an equivalent sphere that had the same average translational diffusion coefficient as the worm-like micelles, yielded substantially larger dimensions (Dm = 125 ± 10 nm) and higher ζ value (+73.2 ± 3.3 nm) for the corresponding nanoassemblies.