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The ring-closing metathesis reaction of dendrimers containing allyl ether end groups is known to rigidify them significantly. Herein we report that polyallylated hyperbranched polyglycerol (HPG) 1 complexes the sodium salt of rose Bengal in chloroform solution but releases it readily to water. In contrast, extensively cross-linking 1 with Grubbs catalyst provides 2 which similarly complexes rose Bengal, but does not release it despite 12 h of shaking with water. Both 1 and 2 also complex thymol blue and exhibit the same differential complex stability when extracted with water. Neither 1 nor 2 complex Congo red sodium salt and more weakly solubilize the cesium salt of rose Bengal and thymol blue. Larger loop size cross-linked analogs HPG 5 and 6 also bind rose Bengal (RB) and thymol blue and are able to bind Congo red, but both release the dye more readily when extracted with water. In addition, a bathochromic shift is observed in the UV spectra for complex 6·RB, suggesting a changed microenvironment for the dye due to a tighter binding of the counter anion. Dihydroxylation of the alkene groups in 1, 2, 5, and 6 produced HPGs 3, 4, 7, and 8, respectively. HPGs 3 and 4 are both water-soluble, but 7 and 8 were not and could not be studied further. In water, HPG 4 solubilized less than one nonpolar guest (Nimodipine, pyrene, or Nile red) per polymer at least in part because it forms very large aggregates. Dynamic light scattering (DLS) and size exclusion chromatography (SEC) indicate aggregates with diameters of ca. 100 nm in pure water. The aggregates dissociated in high salt concentrations suggesting applications in stimuli responsive materials.