Abstract: | Organic solar cells have made rapid progress in the last two decades due to the innovation of conjugated materials and photovoltaic devices. Microphase separation that connects with materials and devices plays a crucial role in the charge generation process. In this account, we summary our recent works of developing new crystalline conjugated polymers to control the microphase separation in thin films in order to realize high performance in solar cells, including crystalline diketopyrrolopyrrole‐based donor polymers, perylene bisimide‐based electron acceptors, and “double‐cable” conjugated polymers that contain covalently‐linked crystalline donor and acceptor in one material for single‐component organic solar cells. |