The low power conversion efficiency (PCE) of tin‐based hybrid perovskite solar cells (HPSCs) is mainly attributed to the high background carrier density due to a high density of intrinsic defects such as Sn vacancies and oxidized species (Sn⁴⁺) that characterize Sn‐based HPSCs. Herein, this study reports on the successful reduction of the background carrier density by more than one order of magnitude by depositing near‐single‐crystalline formamidinium tin iodide (FASnI₃) films with the orthorhombic a‐axis in the out‐of‐plane direction. Using these highly crystalline films, obtained by mixing a very small amount (0.08 m) of layered (2D) Sn perovskite with 0.92 m (3D) FASnI₃, for the first time a PCE as high as 9.0% in a planar p–i–n device structure is achieved. These devices display negligible hysteresis and light soaking, as they benefit from very low trap‐assisted recombination, low shunt losses, and more efficient charge collection. This represents a 50% improvement in PCE compared to the best reference cell based on a pure FASnI₃ film using SnF₂ as a reducing agent. Moreover, the 2D/3D‐based HPSCs show considerable improved stability due to the enhanced robustness of the perovskite film compared to the reference cell.

Organic–inorganic hybrid perovskite solar cells (HPSCs) have achieved an impressive power conversion efficiency (PCE) of 25.2% in 2019. At this stage, it is of paramount importance to understand in detail the working mechanism of these devices and which physical and chemical processes govern not only their power conversion efficiency but also their long‐term stability. The interfaces between the perovskite film and the charge transport layers are among the most important factors in determining both the PCE and stability of HPSCs. Herein, an overview is provided on the recent advances in the fundamental understanding of how these interfaces influence the performance of HPSCs. Firstly, it is discussed how the surface energy of the charge transport layer, the energy level alignment at the interfaces, the charge transport in interfacial layers, defects and mobile ions in the perovskite film, and interfacial layers or at the interfaces affect the charge recombination as well as hysteresis and light soaking phenomenon. Then it is discussed how the interfaces and interfacial materials influence the stability of HPSCs. At the same time, an overview is also provided on the various design strategies for the interfaces and the interfacial materials. At the end, the outlook for the development of highly efficient and stable HPSCs is provided.