The synthesis and characterization of a new family of dendritic surfactants called DendriTAC are described. Two series of single- or double-tailed surfactants containing hydrophobic hydrocarbon or fluorocarbon chains grafted onto Tris-(hydroxymethyl)aminomethane (or TRIS)-derived oligomeric polar heads via a copper(I)-mediated click reaction have been prepared. A total of 13 new dendritic surfactants have been obtained by grafting linear polyTRIS branches of variable average degree of polymerization (DPn) onto a single or double-tailed fluorinated or hydrocarbon chain of variable length, via a dendritic central scaffold of generation G1 or G2. Structural parameters of the surfactant assemblies in solution [radii of gyration (RG), volumeweighted hydrodynamic radii (RH), and aggregation numbers (Nag)] were assessed by small-angle X-ray scattering and dynamic light scattering. Overall, regardless of their tree-like structure (i.e., generation type), length of the headgroup (DPn), and nature (hydrocarbonated or fluorinated, single or double-tail) or length of the hydrophobic chains, self-assembling properties of H/F-DendriTACs are in agreement with usual trends of surfactant assemblies, e.g., as a function of chain length or polar head volume. Thus, thanks to their great structural versatility, H/F-DendriTACs can provide highly tunable self-assembly morphologies that can be adapted to specific applications.