The methodology for controlled synthesis of metal nanocrystals with a face-centered cubic (fcc) structure was summarized, illustrating the key parameters for the shape control in the synthesis. Taking the recent progress in our research group as an example, the facet control of metal nanocrystals was demonstrated. For instance, nanocrystals with various low-index facets can be rationally synthesized by selecting appropriate capping agents; the formation of high-index facets can be achieved on the surface of nanocrystals by activating specific sites for atomic addition. As various surface facets possess different atomic arrangements, they exhibit tunable properties in molecular adsorption and activation, which allow us to tailor their performance in catalysis.