An alternative method for the synthesis of 2-heteroaryl or alkynyl benzo[b]thiophene or furan derivatives via direct palladium-catalyzed cross-coupling of 2-benzo[b]thiophene or furan aluminum with heteroaryl or alkynyl bromides, respectively, has been successfully developed. This case is remarkable as the same catalytic system could simultaneously produce either 2-substituted benzo[ b]thiophene or furan derivatives.