Advanced Strategies of Self‐Assembled Monolayers in Inverted Perovskite Solar Cells: From Molecular Tailoring and Interfacial Engineering to Collective Dipole Modulation in Mixed Monolayers

Self‐assembled monolayers (SAMs) have emerged as critical hole transport materials (HTMs) for high‐performance inverted perovskite solar cells (PSCs), owing to their ability to tailor surface energetics and buried interface chemistry. In this review, we summarize recent advances in SAM engineering for inverted PSCs, focusing on strategies in molecular design and interfacial modification and on emerging mixed SAM concepts. We discuss the structure–property relationships and molecular tailoring of SAM molecules, together with interfacial engineering at the buried interfaces for improving wettability and defect passivation to suppress nonradiative recombination. Particular attention is given to mixed SAM strategies. Despite rapid development of mixed SAM applications, rational guidelines for selecting and combining SAM molecules remain insufficiently established. Therefore, rather than relying on trial‐and‐error optimization, we propose collective dipole engineering as a rational framework for highest occupied molecular orbital level positioning to achieve improved charge carrier transport, without developing entirely new molecular systems. Overall, this review proposes dipole moment modulation as a key parameter linking interfacial chemistry with device physics for guiding selection of SAM combinations. Such collective dipole modulation provides a pathway toward highly efficient and operationally stable inverted PSCs, offering insights into the development of next‐generation HTMs in photovoltaic and optoelectronic applications.