Additives are widely adopted for efficient, stable, and hysteresis‐free perovskite solar cells and play an important role in various breakthroughs of perovskite solar cells (PSCs). Herein the various additives adopted for PSCs are reviewed and their functioning mechanism and influence on device performance is described. The main roles of additives, modulating morphology of perovskite films, stabilizing phase of formamidinium (FA) and cesium (Cs)‐based perovskites, adjusting energy level alignment in PSCs, suppressing nonradiative recombination in perovskites, eliminating hysteresis, enhancing operational stability of PSCs, are summarized.

Power conversion efficiency of perovskite solar cells (PSCs) has been boosted to 25.5% among the highest efficiency for single‐junction solar cells, making PSCs extremely promising to realize industrial production and commercialization. Scaling up PSCs to fabricate efficient perovskite solar modules (PSMs) is the fundamental for applications. Here, present progresses on scaling up PSCs are reviewed. The structure design for PSMs is discussed. Various scalable methods and related morphology control strategies for large‐area uniform perovskite films are summarized. Potential charge transport materials and electrode materials together with their scalable methods for low‐cost, efficient, and stable PSMs are also summarized. Besides, current attempts on encapsulation for improving stability and reducing lead leakage are introduced, and the calculated cost and environment influence of PSMs are also outlined.

The control of film morphology is crucial in achieving high‐performance perovskite solar cells (PSCs). Herein, the crystals of the perovskite films are reconstructed by post‐treating the MAPbI3 devices with methylamine gas, yielding a homogeneous nucleation and crystallization of the perovskite in the triple mesoscopic inorganic layers structured PSCs. As a result, a uniform, compact, and crystalline perovskite layer is obtained after the methylamine gas post‐treatment, yielding high power conversion efficiency (PCE) of 15.26%, 128.8% higher than that of the device before processing. More importantly, this post‐treatment process allows the regeneration of the photodegraded PSCs via the crystal reconstruction and the PCE can recover to 91% of the initial value after two cycles of the photodegradation‐recovery process. This simple method allows for the regeneration of perovskite solar cells on site without reconstruction or replacing any components, thus prolonging the service life of the perovskite solar cells and distinguishing from any other photovoltaic devices in practice.