Photoactive formamidinium lead triiodide (α‐FAPbI3) perovskite has dominated the prevailing high‐performance perovskite solar cells (PSCs), normally for those spin‐coated, conventional n‐i‐p structured devices. Unfortunately, α‐FAPbI3 has not been made full use of its advantages in inverted p‐i‐n structured PSCs fabricated via blade‐coating techniques owing to uncontrollable crystallization kinetics and complicated phase evolution of FAPbI3 perovskites. Herein, a customized crystal surface energy regulation strategy has been innovatively developed by incorporating 0.5 mol% of N‐aminoethylpiperazine hydroiodide (NAPI) additive into α‐FAPbI3 crystal‐derived perovskite ink, which enabled the formation of phase‐pure, highly‐oriented α‐FAPbI3 films. We deciphered the phase transformation mechanisms and crystallization kinetics of blade‐coated α‐FAPbI3 perovskite films via combining a series of in‐situ characterizations. Interestingly, the strong chemical interactions between the NAPI and inorganic Pb‐I framework help to reduce the surface energy of (100) crystal plane by 42%, retard the crystallization rate and lower the formation energy of α‐FAPbI3. The resultant blade‐coated inverted PSCs based on (100)‐oriented α‐FAPbI3 perovskite films realized promising efficiencies up to 24.16% (~26.5% higher than that of the randomly‐oriented counterparts), accompanied by improved operational stability. This result represented one of the best performances reported to date for FAPbI3‐based inverted PSCs fabricated via scalable deposition methods.