The first two asymmetric-indenothiophenebased donor-acceptor copolymers (PITBT and PITFBT) are prepared through Stille coupling reactions between distannyl indenothiophene and brominated benzothiadiazole derivatives. The best performing solar cell fabricated from PITFBT exhibits a power conversion efficiency of 9.14% which demonstrates a great potential of the asymmetric indenothiophene for high-performance copolymers.