We designed and constructed a new family of 608 dendritic dipyridyl donors, from which two novel triangular metallodendrimers were successfully prepared via coordination-driven self-assembly.Inspired by the existence of multiple intermolecular interactions(e.g., p–p stacking and CH–p interactions) imposed by the DMIP-functionalized poly(benzyl ether) dendrons, their hierarchical selfassembly behaviors were studied in various mixed solvents by using scanning electron microscopy(SEM). Interestingly, it was found that the morphologies of the obtained metallodendrimers were highly depended on the dendron generation. For example, the first-generation metallodendrimer was able to hierarchically self-assemble into the spherical nanostructures in various mixed solvents. However, the nanofibers were observed for the second-generation metallodendrimer under the similar conditions.Furthermore, the driven force for the formation of such ordered nanostructures was investigated by using1 H NMR and fluorescence spectroscopy. We designed and constructed a new family of 608 dendritic dipyridyl donors, from which two novel triangular metallodendrimers were successfully prepared via coordination-driven self-assembly. Inspired by the existence of multiple intermolecular interactions (eg, p-p stacking and CH-p interactions ) imposed by the DMIP-functionalized poly (benzyl ether) dendrons, their hierarchical selfassembly behaviors were studied in various mixed solvents by using scanning electron microscopy (SEM). Interestingly, it was found that the morphologies of the obtained metallodendrimers were highly depended on the For example, the first-generation metallodendrimer was able to hierarchically self-assemble into the spherical nanostructures in various mixed solvents. However, the nanofibers were observed for the second-generation metallodendrimer under the similar conditions. Future, the driven force for the formation of such ordered nanostructures was investigated by using1H NMR a nd fluorescence spectroscopy.