<p>Formamidinium lead iodide (FAPbI₃) perovskite is a leading candidate for high-efficiency solar cells, but its application is hindered by the kinetic instability of its α-phase crystallization. Here, a highly effective strategy for directing the ordered crystallization of α-FAPbI₃ in the n-i-p architecture is developed by incorporating a self-assembled molecule (SAM) into the anti-solvent, unlike conventional phosphate-based SAMs requiring polar protic solvents, the -SCN SAM are processed from non-polar, aprotic solvents compatible with perovskite surfaces. An in-situ formed, self-assembled layer acts as a dynamic template, guiding the top-down crystallization process to yield highly ordered α-phase films. Through a series of in-situ measurements, it is rigorously demonstrated that this SAM treatment suppresses undesirable intermediate phases, accelerates the δ-to-α transition, and strategically slows crystal growth, promoting highly ordered films. This meticulously designed strategy culminates in high-quality perovskite films, enabling single-junction devices with a champion power conversion efficiency (PCE) of 26.18% (certified at 25.67%) and mini-modules with a PCE of 21.70%. These results underscore the power of directed self-assembly in fabricating highly efficient and stable n-i-p perovskite solar cells.</p>