Atomically precise graphene nanoribbons (GNRs) have attracted significant attention recently due to their intriguing electronic properties and applications in nextgeneration optoelectronic devices. Their optical and electronic properties strongly depend on their structures, such as lengths, widths, shapes, and edges. Besides control over the above-mentioned structural parameters, properties can be fine-tuned by incorporation of heteroatoms into the conjugated nanoribbon backbones. Organic chemists have focused on developing new synthetic strategies and easily accessible structure-rich building blocks for the production of GNRs as well as heteroatomdoped GNRs over decades. The solution-phase synthesis, that is the formation of a linearly extended precursor followed by a ring-closing step is one of the most promising strategies for the preparation of well-defined GNRs on a large scale. To the study of length-dependent photophysical properties via comparison with their linear counterparts, GNRs with different lengths are usually prepared by iterative synthesis (Figure ). These methods often involve complex and expensive starting materials, restricting structural and functional diversity. Inspired by the "shotgun" approach to macrocycle, which involves using a one-pot multicomponent cyclization of small monomers, to access the macrocycle. This approach shows great advantages to quick constructing different size macrocycle. In addition, phenanthrene as an important polycyclic aromatic hydrocarbon (PAH), which with armchair side. We envision that 1,8-diaryl phenanthrene derivative would be promising building blocks for GNRs, which are readily available. 9 Herein, we report a series of arcuate GNRs with thiophene-backbones, achieved by "Shotgun" approach with high efficiency. The precursor of GNRs was constructed by the Suzuki-Miyaura coupling with 1,8-diaryl phenanthrene as key building block and then dehydrocyclization to obtain GNRs of different lengths. In this case, three GNRs (AR-11, AR-17, and AR-23) with multiple edge structures were achieved (the numbering indicates the number of longitudinally fused rings along their backbone) (Figure ). Oxidizing electron-rich sulfur atoms to electron-deficient sulfones yielded ARO-11 and ARO-17 with high efficiency, respectively. Detailed theoretical and experimental studies demonstrate that length and oxidation state greatly affects not only molecular conformations but also electronic structures and photophysical properties.