Since their earliest synthesis, much interest has arisen in the use of dendritic and structurally allied forms of polymer for light energy harvesting, especially as organic adjuncts for solar energy devices. With the facility to accommodate a proliferation of antenna chromophores, such materials can capture and channel light energy with a high degree of efficiency, each polymer unit potentially delivering the energy of one photon-or more, when optical nonlinearity is involved. To ensure the highest efficiency of operation, it is essential to understand the processes responsible for photon capture and channelling of the resulting electronic excitation. Highlighting the latest theoretical advances, this paper reviews the principal mechanisms, which prove to involve a complex interplay of structural, spectroscopic and electrodynamic properties. Designing materials with the capacity to capture and control light energy facilitates applications that now extend from solar energy to medical photonics. © 2011 by the authors; licensee MDPI, Basel, Switzerland.