LAUSR

All organic charge‐transporting layer (CTL)‐featured perovskite solar cells (PSCs) exhibit distinct advantages, but their scaling‐up remains a great challenge because the organic CTLs underneath the perovskite are too thin to achieve large‐area homogeneous layers by spin‐coating, and their hydrophobic nature further hinders the solution‐based fabrication of perovskite layer. Here, an unprecedented anchoring‐based coassembly (ACA) strategy is reported that involves a synergistic coadsorption of a hydrophilic ammonium salt CA‐Br with hole‐transporting triphenylamine derivatives to acquire scalable and wettable organic hole‐extraction monolayers for p–i–n structured PSCs. The ACA route not only enables ultrathin organic CTLs with high uniformity but also eliminates the nonwetting problem to facilitate large‐area perovskite films with 100% coverage. Moreover, incorporation of CA‐Br in the ACA strategy can distinctly guarantee a high quality of electronic connection via the cations' vacancy passivation. Consequently, a high power‐conversion‐efficiency (PCE) of 17.49% is achieved for p–i–n structured PSCs (1.02 cm2), and a module with an aperture area of 36 cm2 shows PCE of 12.67%, one of the best scaling‐up results among all‐organic CTL‐based PSCs. This work demonstrates that the ACA strategy can be a promising route to large‐area uniform interfacial layers as well as scaling‐up of perovskite solar cells.