High molecular weight polyglycerol-dendronized poly(norbornene)s (PGD-PNBs) were prepared via ring-opening metathesis polymerization of norbornene monomers containing amine functional groups on the side-chains followed by dendron growth from the olefins of PNB backbones using iterative dihydroxylation and allylation. The fourth-generation PGD-PNB with a degree of polymerization of ca. 500 is thus functionalized with 16 peripheral hydroxyl groups as well as a single amine on each repeat unit of the PNB backbone. Furthermore, the amine functionality could be used to install hydrophobic fluorophores such as coumarin and pyrene, thereby obtaining the final PGD-PNB structures which are highly water-soluble and fluorescent.