A new synthetic method for dithieno[3,2-b:2′,3′-d]thiophenes was developed. The approach involves three steps starting from thiophene: tetraiodation of thiophene, selective dialkynylations on the 2,5-positions of the tetraiodothiophene, and finally CuI/TMEDA catalyzed double annulations of 2,5-dialkynyl-3,4-diiodothiophenes by Na 2 S, to afford dithieno[3,2-b:2′,3′-d]thiophene and its derivatives.