Control of the spatial arrangement of atoms over nanoscale dimensions can be used to achieve electronic isolation of chromophores, to control electronic delocalization, to control the spatial variation of material indices of refraction, and to achieve spatially controlled energy transfer. Such control can, in turn, be exploited to avoid quenching of luminescence, to control optical absorption and emission characteristics, to achieve morphological resonances and photonic bandgap phenomena, and to achieve light harvesting and transfer to an active center. Examples of control of optical properties using nanostructured dendimers, block copolymers, and polymer microspheres are given.