This article reviews the motivations for developing polymer-based photovoltaics and describes some of the material systems used. Current challenges are identified, and some recent developments in the field are outlined. In particular, recent work to image and control nanostructure in polymer-based solar cells is reviewed, and very recent progress is described using the unique properties of organic semiconductors to develop strategies that may allow the Shockley–Queisser limit to be broken in a simple photovoltaic cell.