This paper provides direct evidence to support the role of a capping agent in controlling the evolution of Ag seeds into nanocrystals with different shapes. Starting with single-crystal seeds (spherical or cubic in shape), we could selectively obtain Ag octahedrons enclosed by {111} facets and nanocubes/nanobars enclosed by {100} facets by adding sodium citrate (Na(3)CA) and poly(vinyl pyrrolidone) (PVP), respectively, as a capping agent while all other parameters were kept the same. This research not only offers new insights into the role played by a capping agent in shape-controlled synthesis but also provides, for the first time, Ag octahedrons as small as 40 nm in edge length for optical and spectroscopic studies.