The tendency of organic chromophores, such as porphyrins and phthalocyanines, to aggregate via aromatic interactions in water is an important issue since such aggregation can lead to attenuation of the chromophore’s photophysical properties. This talk will illustrate how nanoarchitectures containing well-placed chromophores can be (a) self-assembled in highly competitive aqueous media whilst (b) the individual chromophores are precluded from aggregation via host-guest chemistry. The connecting thread of the talk will be on how hierarchical self-assembly using an array of supramolecular interactions (especially host-guest chemistry, and programmable DNA self-assembly) can be used to construct photoactive ensembles and nanostructures. The beginning section of the seminar will discuss the development of multi-chromophore containing wires, spheres, and thin films. The latter section of the seminar will discuss our recent efforts to prepare photonic systems via synthetically modified DNA oligonucleotides and enzyme co-factors (luciferin).