Surface capping agents have been extensively used to control the evolution of seeds into nanocrystals with diverse but well‐controlled shapes. Here we offer a comprehensive review of these agents, with a focus on the mechanistic understanding of their roles in guiding the shape evolution of metal nanocrystals. We begin with a brief introduction to the early history of capping agents in electroplating and bulk crystal growth, followed by discussion of how they affect the thermodynamics and kinetics involved in a synthesis of metal nanocrystals. We then present representative examples to highlight the various capping agents, including their binding selectivity, molecular‐level interaction with a metal surface, and impacts on the growth of metal nanocrystals. We also showcase progress in leveraging capping agents to generate nanocrystals with complex structures and/or enhance their catalytic properties. Finally, we discuss various strategies for the exchange or removal of capping agents, together with perspectives on future directions.

Despite the pivotal role played by the reduction of a salt precursor in the synthesis of metal nanocrystals, it is still unclear how the precursor is reduced. The precursor can be reduced to an atom in the solution phase, followed by its deposition onto the surface of a growing nanocrystal. Alternatively, the precursor can adsorb onto the surface of a growing nanocrystal, followed by reduction through an autocatalytic process. With Pd as an example, here we demonstrate that the pathway has a correlation with the reduction kinetics involved. Our quantitative analyses of the reduction kinetics of PdCl and PdBr by ascorbic acid at room temperature in the absence and presence of Pd nanocubes, respectively, suggest that PdCl was reduced in the solution phase while PdBr was reduced on the surface of a growing nanocrystal. Our results also demonstrate that the reduction pathway of PdBr by ascorbic acid could be switched from surface to solution by raising the reaction temperature.