Abstract3‐Halobithienyls have been prepared through the Pd(PPh3)4‐catalyzed coupling of thiopheneboronic acids with 2,4‐dihalothiophenes. The ring‐opening of the corresponding 3‐lithiobithienyls obtained upon halogen‐metal exchange with phenyllithium has been investigated. Compound12, 3′‐iodo‐2,2′,2″‐terthienyl, was prepared in one step through the Pd(PPh3)4‐catalyzed coupling of two equivalents of 2‐thiopheneboronic acid with 2,3,5‐triiodothiophene. Treatment of12with phenyllithium and methyl iodide gave a mixture of compounds10and11occurring