Coordination‐driven hierarchical assembly represents an emerging and significant research area for the fabrication of hybrid nanostructures based on 2D materials. This review highlights the latest progress in this regime, focusing on the synthesis approaches, various architectures, and structure–property relationship. Moreover, insights in the present challenges and possible future research directions are also discussed. Abstract 2D materials have received tremendous scientific and engineering interests due to their remarkable properties and broad‐ranging applications such as energy storage and conversion, catalysis, biomedicine, electronics, and so forth. To further enhance their performance and endow them with new functions, 2D materials are proposed to hybridize with other nanostructured building blocks, resulting in hybrid nanostructures with various morphologies and structures. The properties and functions of these hybrid nanostructures depend strongly on the interfacial interactions between 2D materials and other building blocks. Covalent and coordination bonds are two strong interactions that hold high potential in constructing these robust hybrid nanostructures based on 2D materials. However, most 2D materials are chemically inert, posing problems for the covalent assembly with other building blocks. There are usually coordination atoms in most of 2D materials and their derivatives, thus coordination interaction as a strong interfacial interaction has attracted much attention. In this review, recent progress on the coordination‐driven hierarchical assembly based on 2D materials is summarized, focusing on the synthesis approaches, various architectures, and structure–property relationship. Furthermore, insights into the present challenges and future research directions are also presented.

Published in: "Small".