Narrow‐bandgap (NBG) perovskites have attracted significant attention for their promising potential as light‐absorbing materials in tandem solar cells. However, tin‐lead mixed perovskites face a major limitation of the facile oxidation of Sn2⁺, leading to Sn vacancies in the perovskite films. In this study, sodium triacetoxyborohydride (STAB) is introduced as an antioxidant, while potassium (5‐bromo‐2‐fluoropyridin‐3‐yl)trifluoroborate (PBFT) is employed as a surface modifier for mixed tin‐lead perovskites. This combined approach not only suppresses Sn2⁺ oxidation but also promotes the formation of high‐quality perovskite films. Furthermore, the induced energy band bending at the perovskite/C60 interface substantially enhances charge transfer. Consequently, the optimized device achieves a power conversion efficiency (PCE) of 23.41% with excellent illumination stability. When paired with a wide‐bandgap (WBG) semi‐transparent perovskite solar cell (PSC), the resulting four‐terminal (4‐T) all‐perovskite tandem solar cell attains a remarkable efficiency of 27.37%.