Abstract Organic solar cells (OSCs), as a third‐generation photovoltaic technology, have now achieved power conversion efficiencies exceeding 21.0%, reaching the commercialization threshold. This great progress is largely attributed to innovations in materials design. Aromatic diimides (ADIs), as electron‐accepting moieties, are extensively studied in OSC research owing to their high electron affinity, superior electron mobility, and facile chemical modification. Notably, over the past 3 years, ADI‐based molecular designs have dominated the development of cathode interlayer materials (CIMs), enabling the breakthrough of OSC efficiencies. Therefore, this review comprehensively surveys recent advances in ADI‐based CIMs, including naphthalene diimides, perylene diimides, and their fused structures. Finally, future development trends and practical prospects are discussed for these materials, aiming to elucidate the critical role of ADI‐based CIMs in advancing OSC technology and inspire future innovations in the field.