Gan Xu, Yang Yang, Qiongyao Chen, Su‐Yuan Xie, Qianyan Zhang
ABSTRACT While planar π‐conjugated molecules have long dominated organic electronics, their strong aggregation tendencies often compromise processability and performance. In contrast, bowl‐shaped π‐conjugated molecules (buckybowls) have emerged as a unique class of semiconductors, with intrinsic curvature endowing them with enhanced solubility, permanent dipole moments, and distinctive 3D packing motifs. This review comprehensively summarizes recent advances in the molecular design of buckybowls, focusing on strategies such as π‐extension, peripheral functionalization, and heteroatom doping to precisely tune their optoelectronic properties and solid‐state organization. The discussion systematically connects these molecular designs to their performance in key organic electronic devices, including organic field‐effect transistors ( OFET s), organic light‐emitting diodes ( OLED s), organic solar cells ( OSC s), and perovskite solar cells ( PSC s). The review highlights the profound structure‐packing‐property relationships that underpin device efficiency and stability, demonstrating how curvature‐directed interactions can be harnessed for high‐performance applications. Finally, we provide a perspective on the current challenges and future opportunities in this rapidly evolving field, aiming to guide the rational design of curved organic semiconductors for next‐generation optoelectronic technologies.