LAUSR

Metal halide perovskites constitute a new class of semiconductors that are structurally tailorable, exhibiting rich structural polymorphs. In this perspective, the polymorphism in lead halide perovskites is described—a material system currently used for high‐performance photovoltaics and optoelectronics. Strategies for stabilizing the metastable perovskite polymorphs based on crystal size reduction and surface functionalization are critically reviewed. Focus is on an unprecedented stabilization of metastable perovskite lattices in the 2D limit (e.g., with a thickness down to a few unit cells) due to the dominance of surface effects. This stabilization allows the incorporation of various A‐cations that deemed oversized for 3D perovskites into the 2D perovskite lattices, which bring new insights on the relationships between the crystal structures and optoelectronic properties and lead to emergent ferroelectricity in halide perovskites. A comprehensive understanding is provided on how the A‐cations influence the structural, optoelectronic, and ferroelectric properties, with an emphasis on the second order Jahn‐Teller distortion caused by the oversized A‐cations. Finally, future perspectives on new structure exploration and studies of fundamental photophysical properties using stabilized perovskite lattices are provided.