Tilted Lattice Stacking of Layered Hydrogen‐Bonded Organic Framework Colloidal Particles Promotes Charge Separation and Boosts the Efficiency of Perovskite Solar Cells

Defect passivation using aromatic molecules is an effective strategy to suppress trap states and non‐radiative recombination in perovskite solar cells (PSCs). However, the correlation between molecular configuration and interfacial carrier dynamics remains elusive, as prior studies largely focus on adsorption strength and energy‐level alignment while neglecting adsorption regularity and configurational completeness at grain boundaries. Herein, 2,4,6‐tri(1H‐pyrazol‐4‐yl)pyridine (PYTPZ) is introduced as a grain‐boundary passivator. PYTPZ molecules are preorganized into nanoscale hydrogen‐bonded organic frameworks, enabling controllable configuration. The exposed peripheral functional groups induce a tilted lattice stacking with perovskite, forming an ordered “standing” configuration with reduced steric hindrance and enhanced interfacial coverage. This geometry localizes the passivator HOMO and aligns excited‐state transitions with interfacial charge transfer, thereby promoting charge separation. In contrast, a “lying” configuration leads to excessive orbital overlap and ineffective hole trapping. Consequently, the standing configuration facilitates efficient hole extraction and suppresses non‐radiative recombination, delivering a champion efficiency of 25.63% (24.85% for 1 cm 2 devices) with markedly improved stability.