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The rapid synthesis of structurally complicated electron donors & acceptors still remains a major challenge in organic solar cells (OSC). In this work, we developed a highly efficient strategy to access long‐chain oligomeric donor and acceptors for OSC applications. A series of cyclopentadithiophene (CPDT) and benzothiadiazole (BT)‐based π‐conjugated oligomers, i.e., three oligomeric acceptors...