Abstract: Perovskite solar cells are now among the most promising photovoltaic industries. Novel passivation materials are emerging, and self-polymerizing functional materials have proven highly effective in perovskite solar cell optimization. Adding these materials can regulate perovskite crystallization, passivate surface defects, and form hydrophobic layers, greatly boosting device efficiency and environmental stability. This paper offers a systematic review of self-polymerizing materials, focusing on their types, mechanisms, and research progress in perovskite solar cells. It emphasizes their key roles in defect passivation, interface engineering, and stability enhancement. However, challenges remain in the scaled preparation, long - term stability, and adaptability of these materials to complex conditions. Continued innovation in self-polymerizing materials is expected to fast - track the commercialization of perovskite solar cells and propel photovoltaic technology forward.