A versatile synthetic route involving the use of organotin compounds has been applied for the preparation of functionalized oligothiophenes. Thus, substituted α-bithiophenes have been synthesized via the coupling reaction of 2-bromothiophenes with 2-trimethylstannylthiophene. The latter reagent couples with 2,5-dibromothiophenes to give the α-terthiophenes which are also accessible through the reaction of 5-trimethylstannyl-α-bithiophene with 2-bromothiophenes. 2,5-Bis(trimethylstannyl) thiophene and 5,5′-bis(trimethylstannyl)-α-bithiophene react with 2-bromothiophenes to give α-terthiophenes and α-quaterthiophenes, respectively. α-Quaterthiophene is also produced via the reaction of 5-trimethylstannylthiophene with 5,5′- dibromo-α-bithiophene. The coupling reaction of 5-tnmethylstannyl-α-bithiophene with 2.5-dibromothiophene affords the α-quinquethiophene. The structures of the new compounds were confirmed by elemental analysis, Mass spectrometry,1H- and13CNMR spectral data.