Bulk-heterojunction polymer solar cells have emerged as an attractive type of cost-effective solar energy–electrical power transforming device. Recently, great progress in the development of new photo-harvesting materials and device optimizations have been achieved in this field, resulting in the significant improvement of the power conversion efficiencies of polymer solar cells from around 1% to higher than 8.0%. The rational design and fine tailoring of the molecular structures of donor polymers significantly contributed to these prominent advances. Among all kinds of donor polymers, push–pull conjugated polymers, which consist of alternating electron-rich and electron-deficient units have been most extensively developed and have dominated the library of donor materials for polymer solar cells, because their intrinsic optical and electronic properties can be readily tuned to the desired situation by controlling the intramolecular charge transfer from donor unit to acceptor unit. This review provides a brief overview of the recent development of push–pull conjugated polymers and their application in solar cells. The relationships between the materials' chemical structures and properties, such as absorption spectra, energy levels, mobilities and photovoltaic behaviors, were also discussed.