An unprecedented example for the selective and efficient synthesis of an FBT–thiophene structural motif via dual C–H functionalization, catalyzed by palladium, has been developed. Fluorinated benzotriazole is also applicable to the reaction. This protocol provides facile access to unsymmetrical and symmetrical thienylated FBTs that can be applied in the development of high performance photovoltaics, in particular in bulk heterojunction (BHJ) solar cells.