An N-annulated indenoperylene electrondonor decorated with photochemically inactive segments is synthesized and further conjugated via triple bond with electron-acceptor benzothiadiazolylbenzoic acid for a metal-free donor/acceptor dye. Without use of any coadsorbate, the judiciously tailored indenoperylene dye achieves a high-power conversion efficiency of 12.5% under irradiance of 100 mW cm(-2) AM1.5G sunlight.