Four potential semiconductors containing benzo[1,2-b:4,5-b’]dithiophene were successfullysynthesized via Heck-type coupling reaction. The best condition of the arylation was optimized. Theselectivity of the first and second arylation at positions 9 and 10 were elucidated with HMBC spectrumand X-ray analysis.Keyword: BDT, dithiophene, benzo dithiophene, Heck coupling reaction, semiconductor