AbstractLow‐temperature solution processing of the perovskite layer enables the fabrication of flexible devices. However, the performance of flexible perovskite solar cells (f‐PSCs) lags far behind their rigid counterpart in terms of efficiency and stability. Emerging evidence demonstrates that the quality of the buried interface between perovskite and transporting layer underneath is the key point. Herein, a class of novel halide substituted ammonium salts, i.e., n‐bromophenethylammonium (n‐Br‐PEAX, n = 2 or 4, X = Cl or Br) are designed and synthesized to modify the buried interface as well as the perovskite crystallization of f‐PSCs. It is found that the ammonium salt with rational design molecular structure can modify the crystallization speed of perovskite, leading to the formation of a compact and uniform morphology without nanovoids at the interface. As a result, the efficiency of f‐PSCs is improved from 15.4% to 20.2%. Moreover, the modified devices without encapsulation retain 86% of their initial performance after 1000 h of aging at ambient conditions and 87% after 290 h of continuous operation.