The synthesis and optimization of new photovoltaic donor polymers is a time-consuming process. Computer-based molecular simulations can narrow the scope of materials choice to the most promising ones, by identifying materials with desirable energy levels and absorption energies. In this paper, such a retrospective analysis is presented of a series of fused aromatic push-pull copolymers. It is demonstrated that molecular calculations do indeed provide good estimates of the absorption energies measured by UV-vis spectroscopy and of the ionization potentials measured by photoelectron spectroscopy in air. Comparing measured photovoltaic performance of the polymer series to the trend in efficiencies predicted by computation confirms the validity of this approach. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.