Poly[bis(4‐phenyl)(2,4,6‐trimethylphenyl)amine (PTAA) is one of the most efficient hole transport materials for p–i–n structured perovskite solar cells (PSCs). However, the hydrophobicity of PTAA causes wettability problems and is thereby associated with low yield and poor reproducibility. Herein, a new strategy for improving the perovskite precursor wettability on PTAA is developed. A Cu2(Thiourea)Br2 complex interfacial layer is introduced on the PTAA, improving the coverage of perovskite precursors and thereby the perovskite film. Partially dissolved Cu2(Thiourea)Br2 in the perovskite absorber further enhances band alignment and carrier extraction between layers. With the addition of Cu2(Thiourea)Br2 layer on nondoped PTAA, PSCs in p–i–n structure with a bandgap of 1.63 eV have achieved over 21% efficiency both on 0.1 and 1.0 cm2 sized devices with a significantly improved yield and reproducibility. Unencapsulated devices retain 100% of their initial efficiency after 2000 h at 65 °C.