Our work suggests that dendritic macromolecules studied herein exist in the form of aggregated self-assembled structures in aqueous phase and these aggregates have been clearly viewed by surface topography. In the presence of ionic surfactants, the macromolecules show significant interactions both with the monomeric and micellar species due to the electrostatic interactions, which become more clearer under the pH effect. The cationic surfactants show strong electrostatic interactions in the basic medium, while anionic surfactants demonstrate this behavior in the acidic medium. The nature of head group as well as counter ion demonstrates a clear influence on the magnitude of dendrimer-surfactant interactions. The cationic surfactant with dimeric nature and bromide counter ion demonstrate much stronger interactions with both amine and ester terminated generations of PAMAM.