The Rise of Perovskitoid for Photoelectric Device: From Preparation to Applications

Perovskitoids have attracted widespread attention in recent years by extending octahedral connectivity, thereby overcoming the traditional 3D perovskite materials’ limitations on the tolerance factor, expanding structural diversity, and enhancing stability and bandgap tunability. This review first summarizes the advanced preparation methods for high‐quality perovskitoid single crystals. Subsequently, we systematically classify perovskitoids into 0D, 1D, 2D, and 3D structures based on their dimensionality, elaborating on the relationship between their unique octahedral connectivity modes and optoelectronic properties. Furthermore, advances in perovskitoids for optoelectronic applications are highlighted, with a focus on their roles in solar cells, light‐emitting devices, and detectors. Finally, to address current bottlenecks, we propose future perspectives to accelerate their practical commercialization.