Abstract Global efforts and synergetic interdisciplinary collaborations on solution-processed bulk-heterojunction polymer solar cells (PSCs or OPVs) made power conversion efficiencies over 10% possible. The rapid progress of the field is credited to the synthesis of a large number of novel polymers with specially tunable optoelectronic properties, a better control over the nano-morphology of photoactive blend layers, the introduction of various effective interfacial layers, new device architectures and a deeper understanding of device physics. We will review the pioneering materials for polymer–fullerene solar cells and trace the progress of concepts driving their development. We discuss the evolution of morphology control, interfacial layers and device structures fully exploring the potential of photoactive materials. In order to guide a further increase in power conversion efficiency of OPV, the current understanding of the process of free charge carrier generation and the origin of the photovoltage is summarized followed by a perspective on how to overcome the limitations for industrializing PSCs.