The synthesis of conjugated rod–coil block copolymers generally requires the combination of two different polymerization techniques. A two-stage approach was commonly used to synthesize such block copolymers. The first stage involves the synthesis of a soluble conjugated block with a proper functionality and then coupling with the coil block by another reaction, such as living polymerization. The critical issue for such synthesis is the preparation of soluble conjugated rods with a desired chain end functionality for a stepwise synthesis.