Abstract Post‐treatment is an essential passivation step for the state‐of‐the‐art perovskite solar cells (PSCs) but the additional role is not yet exploited. In this work, perovskite film is fabricated under ambient air with wide humidity window and identify that chloride redistribution induced by post‐treatment plays an important role in high performance. The chlorine/iodine ratio on the perovskite surface increases from 0.037 to 0.439 after cyclohexylmethylammonium iodide (CHMAI) treatment and the PSCs deliver a champion power conversion efficiency (PCE) of 24.42% (certificated 23.60%). The maximum external quantum efficiency of electroluminescence (EQE EL ) reaches to 10.84% with a radiance of 170 W sr −1 m −2 , forming the reciprocity relation between EQE EL and nonradiative open‐circuit voltage loss (86.0 mV). After thermal annealing, 2D component of perovskite will increase while chloride decline, leading to improved photovoltage but reduced fill factor. Hence, it distinguishes that chloride enrichment can improve charge transport/recombination simultaneously and 2D passivation can suppress the nonradiative recombination. Moreover, CHMAI can leverage their roles in charge transport/recombination for better performance than phenylethylammonium iodide (Cl/I = 0.114, PCE = 23.32%), due to the stronger binding energy of Cl − . This work provides the insight that the chloride fixation can improve the photovoltaic performance.