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Recent progress in the development of polymer solar cells has improved power-conversion efficiencies from 3% to almost 9%. Based on semiconducting polymers, these solar cells are fabricated from solution-processing techniques and have unique prospects for achieving low-cost solar energy harvesting, owing to their material and manufacturing advantages. The potential applications of polymer solar cells are broad, ranging from flexible solar modules and semitransparent solar cells in windows, to building applications and even photon recycling in liquid-crystal displays. This Review covers the scientific origins and basic properties of polymer solar cell technology, material requirements and device operation mechanisms, while also providing a synopsis of major achievements in the field over the past few years. Potential future developments and the applications of this technology are also briefly discussed.