Lead-based perovskite solar cells (PSCs) have gained considerable interest since 2009 owing to their excellent optical and electrical properties, achieving a certified efficiency of 25.5% over a 12-year period. However,...

Tin perovskites with narrow bandgap and high carrier mobility are highly attractive for environmentally friendly perovskite solar cells (PSCs), but the Sn-based PSCs are still less efficient and stable owing...

Inverted perovskite solar cells (PSCs) often employ triphenylamine‐based materials, such as poly(triarylamine) (PTAA), as hole‐transporting layer (HTL). However, the high hydrophobic PTAA usually induces unsatisfactory perovskite growth, resulting in inferior efficiency and reproducibility. Herein, the vanadium oxide (VOx) film is introduced to modify hydrophobic PTAA layer and establish a hydrophilic surface for high‐quality perovskite film due to the decreased surface tension with improved perovskite solution spread, nucleation, and growth. The PSCs based on PTAA/VOx HTL exhibit high power conversion efficiency up to 18.9% with a sharp increase in comparison to the 16.5% of the control device. Moreover, the reproducibility is also significantly improved, showing a much smaller standard deviation of 1.75 for 40 devices compared to the control devices of 3.64. This work demonstrates that the introduction of VOx is a promising approach in producing high‐quality perovskite films on poor‐wetting PTAA layer for high‐performance inverted PSCs.