The synthesis of a series of dithienosilole–benzotriazole donor–acceptor statistical copolymers with various donor–acceptor ratios is reported, prepared by Kumada catalyst‐transfer polymerization. Statistical copolymer structure is verified by 1H NMR and optical absorption spectroscopy, and supported by density functional theory (DFT) calculations. The copolymers exhibit a single optical absorption band that lies between dithienosilole and benzotriazole homopolymers, which shifts with varying donor–acceptor content. A chain extension experiment using a partially consumed benzotriazole solution as a macroinitiator followed by addition of dithienosilole leads to the synthesis of a statistical dithienosilole–benzotriazole block copolymer from a pure benzotriazole block, demonstrating that both chain extension and simultaneous monomer incorporation are possible using this methodology.
