Single crystalline gold nanorods (ALL NRs) dominated by {110} side facets were employed as seeds to tailor the deposition of Ag. Apart from homogeneous coating, anisotropic coating of Ag was observed and resulted in an orange slice-like shape for the Au@Ag nanocrystal. Different growth rates for the {110} side facets were responsible for this shape: among the four {1 10} facets, two of the neighboring {110} facets grew more quickly and another two grew more slowly, thus inducing the anisotropic deposition of Ag around the Au NR. This growth behavior is believed to be a consequence of competition between the strong stabilization of cetyltrimethylammomium bromide (CTAB) molecules to the {110} facets of Ag and minimization of the overall surface energy. Although the reason for the anisotropic coating remains to be clarified, our results lead to one important conclusion: The interaction of CTAB and metal can be utilized to tune the shapes of bimetallic structures.