Different from the traditional multi-step synthesis, a chemoselective direct C–H arylation is reported for the single-step synthesis of various useful π–acceptor–π (π–A–π) type building blocks for use in organic electronics. This well-optimized C–H heteroarylation exhibits good product yields, broad substrate scope, and high functional group compatibility. Applications in the efficient synthesis of a new metal-free dye sensitizer for dye-sensitized solar cells (DSSCs) are also demonstrated. (Figure presented.).