Flexible perovskite solar cells (f‐PSCs) have attracted great attention due to their promising commercial prospects. However, the performance of f‐PSCs is generally worse than that of their rigid counterparts. Herein, it is found that the unsatisfactory performance of planar heterojunction (PHJ) f‐PSCs can be attributed to the undesirable morphology of electron transport layer (ETL), which results from the rough surface of the flexible substrate. Precise control over the thickness and morphology of ETL tin dioxide (SnO2) not only reduces the reflectance of the indium tin oxide (ITO) on polyethylene 2,6‐naphthalate (PEN) substrate and enhances photon collection, but also decreases the trap‐state densities of perovskite films and the charge transfer resistance, leading to a great enhancement of device performance. Consequently, the f‐PSCs, with a structure of PEN/ITO/SnO2/perovskite/Spiro‐OMeTAD/Ag, exhibit a power conversion efficiency (PCE) up to 19.51% and a steady output of 19.01%. Furthermore, the f‐PSCs show a robust bending resistance and maintain about 95% of initial PCE after 6000 bending cycles at a bending radius of 8 mm, and they present an outstanding long‐term stability and retain about 90% of the initial performance after >1000 h storage in air (10% relative humidity) without encapsulation.

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It is highly desirable to develop large‐scale, low‐cost fabrication processes for flexible perovskite solar cells (f‐PSCs) under ambient conditions for accelerating their potential commercialization. Roll‐to‐roll (R2R) printing technology enables high‐output manufacturing and is well suited for commercially processing f‐PSCs. Herein, triple‐cation f‐PSCs are developed with a planar heterojunction structure consisting of polyethylene‐2,6‐naphthalate/indium tin oxide/SnO2/perovskite/spiro‐OMeTAD/Ag via a combination of R2R microgravure printing and slot‐die coating under ambient conditions with a relative humidity of ≈40%. A mixture of isopropanol and water is used to dilute an as‐purchased SnO2 colloid solution and modify the contact between the electron‐transport layer (ETL) and substrate, leading to a smooth morphology of the R2R‐printed ETL SnO2 layer. Furthermore, suitable intrinsic organic salt additives and the N2 gas blowing‐assisted process are introduced to effectively improve the crystallization of the perovskite, resulting in a high‐quality perovskite film via R2R. After the optimization, the f‐PSCs based on the R2R‐printed ETL SnO2 and the perovskite film under an ambient condition show a power conversion efficiency (PCE) of up to 10.56% and an average PCE of 9.97%. This study provides a potential strategy for commercially fabricating f‐PSCs via a scalable and efficient R2R printing process.