Abstract Methods for the regioselective cross-coupling of 2, 3, 5-tribromothiophene have been developed in which selective aryl–aryl coupling occurs at the 5-position with yields up to 63%. The difference in reactivity of the α-and β-positions then allows sequential regioselective couplings first at the 2-position, followed by the 3-position. Such regioselective cross-coupling allows unprecedented control in the generation of ...