AbstractThe interface and crystallinity of perovskite films play a decisive role in determining the device performance, which is significantly influenced by the bottom hole‐transporting material (HTM) of inverted perovskite solar cells (PVSCs). Herein, a simple design strategy of polymer HTMs is reported, which can modulate the wettability and promote the anchoring by introducing pyridine units into the polyarylamine backbone, so as to realize efficient and stable inverted PVSCs. The HTM properties can be effectively modified by varying the linkage sites of pyridine units, and 3,5‐linked PTAA‐P1 particularly demonstrates a more regulated molecular configuration for interacting with perovskites, leading to highly crystalline perovskite films with uniform back contact and reduced defect density. Dopant‐free PTAA‐P1‐based inverted PVSCs have realized remarkable efficiencies of 24.89% (certified value: 24.50%) for small‐area (0.08 cm²) as well as 23.12% for large‐area (1 cm²) devices. Moreover, the unencapsulated device maintains over 93% of its initial efficiency after 800 h of maximum power point tracking under simulated AM 1.5G illumination.