Holding novel physical properties, high flexibility and strong integration ability with Si‐based electronic devices, two‐dimensional (2D) non‐layered materials have received considerable attentions in recent years. To achieve the 2D anisotropic growth, various strategies have been developed. And a variety of applications have been demonstrated. This review provides an overview on the recent progress of this material family. The scope will cover the preparation strategies, including dry methods and wet chemical approaches, as well as the applications in catalysis, energy conversion and storage, optoelectronic devices and topological crystalline insulators. Conclusion and future perspectives are also given.