摘要： 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.