A new concept for the synthesis of hyperbranched macromolecules involving the use of AB(x) macromonomers containing linear oligomeric units is introduced. This methodology is used for the preparation of a series of novel hyperbranched poly(ethylene glycol) derivatives containing linear poly(ethylene glycol) units of varying lengths and 3,5-dioxybenzoate branching units. An interesting feature of the hyperbranched poly(ethylene glycol) derivatives is their lack of crystallinity, which is used in the design of a new class of polyelectrolyte materials. The dependence of the ionic conductivity on temperature and the concentration of added lithium cations for these novel hyperbranched macromolecules is reported.