An approach combining DNA nanoscaffolds with supramolecular polymers for the efficient and directional propagation of light‐harvesting cascades has been developed. A series of photonic wires with different arrangements of fluorophores in DNA‐organized nanostructures were linked to light‐harvesting supramolecular phenanthrene polymers (SPs) in a self‐assembled fashion. Among them, a light harvesting complex (LHC) composed of SPs and a photonic wire of phenanthrene, Cy3, Cy5 and Cy5.5 chromophores reveals a remarkable energy transfer efficiency of 59%. Stepwise transfer of the excitation energy collected by the light‐harvesting SPs via the intermediate Cy3 and Cy5 chromophores to the final Cy5.5 acceptor proceeds by a Förster resonance energy transfer mechanism. In addition, the light‐harvesting properties are documented by antenna effects ranging from 1.4 up to 23 for different LHCs.
