.alpha.-Quaterthiophene (1), .alpha.-sexithiophene (2), and .alpha.-octithiophene (3) (the highest member of .alpha.-oligothiophenes ever synthesized) were prepared from .alpha.-bithiophene, .alpha.-terthiophene, and .alpha.-quaterthiophene, respectively, via monobromination with N-bromosuccinimide followed by reductive coupling reaction with an activated nickel (0) reagent.