The lesson we learnt from this combined study was that changing both the length (C16G0 < C16SPD < SPM) and/or the charge (+2, +2, +3) of the amphiphilic dendron polar heads had a moderate effect on the affinity of the respective self-assembled dendrimers on heparin binding (CE50 = 0.69, 0.34, and 0.49 for C16G0, C16SPD, and C16SPM). At the same time, we confirmed that in these interactions the electrostatic ion-ion binding depends not only on the heparin and/or micelle charge densities but also from the polyanion and the self-assembled dendrimers structural details. Yet, given the higher CMC values of C16SPD (51 µM) with respect to C16G0 (40 µM), coupled with its slightly lower water solubility and in any case a heparin binding affinity lower that the “lead” compound C22G1 (CMC = 4 µM, CE50 = 0.28, Section 3.1), we decided to employed again the simpler test amphiphilic molecule C16G0 in further studies, as described below.