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Metal nanoclusters are unique nanomaterials, bridging the gap between metal atoms (or metal chelates) and metal nanoparticles. They feature ultra-small size, atomically precise structure, and diversified metal–metal and metal–ligand interactions. Especially, as a metal catalyst, they combine the advantages of their homogeneous and heterogeneous metal analogs, demonstrating potentially high activity, unique selectivity, and recyclability. With the rapid development of synthetic chemistry of metal nanoclusters, they have been discovered as emerging catalysts in many cata-lytic processes, such as hydrogenation, oxidation, borylation, and cross-coupling reactions. Additionally, owing to their exceptional energy and electron transfer capability, they have been combined with photo-, electro-, and enzyme-catalysis, triggering efficient organic transformations. With the development of metal nanocluster chemistry and their application as an emerging catalyst in a lot of efficient even new transformations, the book focusing on metal nanocluster catalysis is in high demand. Based on this situation, we presented this book entitled Metal Nanocluster Catalysis: From Fundamentals to Applications, systematically introducing the formation, structural features, catalytic properties, and mechanisms of this kind of emerging nanomaterial. Chapter 1 gives a brief introduction of metal nanocluster catalysis from aspects of catalytic activity, selectivity, and mechanism. Chapters 2–7 cover three kinds of metal nanoclusters that have been widely employed in catalysis: (i) in situ generated metal nanoclusters, which are spontaneously formed by metal catalysts during the reaction; (ii) supported metal nanoclusters, which are obtained by loading the active metal nanoclusters on relatively robust supports, such as carbon nanomaterials (e.g. carbon nanotube, graphene), metallic oxides (e.g. TiO2, SiO2, CeO2), etc.; (iii) organic ligand-protected metal nanoclusters, which have defined molecular formulas and atomically precise structures, and can be designed and synthesized by wet-chemical reduction methods and other recently developed methods. We intro-duce each metal nanocluster catalysis from their formation processes to their unique structures, and then to their catalytic performance and catalytic mechanisms. Apart from the introduction of the three kinds of metal nanoclusters and their metal catalytic performance, we describe their catalytic activities in photo-, electro-, and enzyme-mediated processes as well, which are included in Chapters 8–10. The practical applications of metal nanocluster catalysis, including large scale Preface viii synthesis, recyclability, and industrial catalysis are presented in Chapter 11. Finally, comments on opportunities and challenges of metal nanocluster catalysis are listed at the end of the book, Chapter 12.This book would be useful for the audiences to understand the current progress as well as the fundamental theory on metal nanocluster catalysis. It can be a handbook for the researchers who are going to start their research in this area, and can also be of value to chemists long involved in metal nanocluster in both academic and industrial research.