Conjugated polymers have been widely prepared using conventional coupling reactions, such as Suzuki, Yamamoto, and Stille coupling reactions. For the grafting-from method, the end-capping procedures of conjugated polymers have been applied for controlling the molecular weight as well as modifying the reactive functionality at the chain ends. The end-functionalized conjugated polymer blocks could then be used as macroinitiators in further polymerization to generate coil blocks, such as vinyl chain ends for anionic polymerization or bromide/chloride ends for atomic transfer radical polymerization (ATRP). On the other hand, the end-functionalized coil segments were also employed to polymerize rod blocks by the grafting-from methods. For the second method, rod and coil blocks with specific functional end groups were prepared individually first and then coupled together by further condensation reactions.