Electron donor–acceptor triblock and diblock copolymers have attracted considerable interest due to their potential applications in all-polymer solar cells as single-active components or surfactants. However, the number of donor–acceptor block copolymers has lagged behind that of the rod–coil and rod–rod block copolymers due to their synthetic difficulties. This minireview highlights the recent advances in the synthetic strategies for the all-conjugated donor–acceptor block copolymers and their application in all-polymer solar cells.