Linear polymeric core, polyethylenimine (PEI), is successfully dendronized divergently using different-generation polyamidoamine (PAMAM)-type dendrons. The formed dendronized polymers are further end-capped using long alkyl acrylate, hexyl acrylate, to give macromolecular amphiphiles, which perform as unimolecular nanocontainers, capable of encapsulating water-soluble dye in their interiors. The encapsulation properties are found to be generation-dependent, in which, at higher generations of nanocontainers, the cavity becomes more localized, due to dense packing of the dendrons at their termini.