Two-dimensional (2D) materials exhibit a wide range of atomic structures, compositions, and associated versatility of properties. Furthermore, for a given composition, a variety of different crystal structures (i.e., polymorphs) can be observed. Polymorphism in 2D materials presents a fertile landscape for designing novel architectures and imparting new functionalities. The objective of this Review is to identify the polymorphs of emerging 2D materials, describe their polymorph-dependent properties, and outline methods used for polymorph control. Since traditional 2D materials (e.g., graphene, hexagonal boron nitride, and transition metal dichalcogenides) have already been studied extensively, the focus here is on polymorphism in post-dichalcogenide 2D materials including group III, IV, and V elemental 2D materials, layered group III, IV, and V metal chalcogenides, and 2D transition metal halides. In addition to providing a comprehensive survey of recent experimental and theoretical literature, this Review identifies the most promising opportunities for future research including how 2D polymorph engineering can provide a pathway to materials by design.