Dendrimers up to three generations, possessing internal PEG units within the branching framework, were synthesized by a convergent approach via the reaction of amine-based dendrons 6, 9, and 11 with 6,6-bis(4-chlorocarbonyl-2-oxabutyl)-4,8-dioxaundecane-1,11-dicarbonyl chloride. These new constructs were fully characterized, shown to exhibit good solubilities in organic as well as aqueous solvents, and demonstrated to solubilize lithium triflate salts in nonaqueous environments, such as chloroform.