ABSTRACT As a potent interfacial platform at the crossroads of molecular engineering and device physics, self‐assembled monolayers (SAMs) have been demonstrated to enable molecular‐level control over buried interfaces in perovskite solar cells (PSCs), whilst overcoming the intrinsic limitations of conventional charge transport layers (CTLs). Over the past two years, SAM‐enabled interface engineering has supported further efficiency gains, with certified efficiencies exceeding 27% for PSCs and 34