There have been many efforts on the generating metal nanocrystals enclosed by high-index facets for the use as highly active catalysts. This paper describes a facile synthesis of Au trisoctahedra with high-index facets. In brief, the Au trisoctahdra were prepared by reduction of $HAuCl_4$ in N,N-dimethylformamide (DMF) containing poly (vinyl pyrrolidone) (PVP) and trace amount of $AgNO_3$. The Ag ions in the reaction solution played a critical role in controlling the trisoctahedral shape of the final product by underpotential deposition (UPD) on the Au surfaces. The as-prepared Au trisoctahedra were single crystal and enclosed by high-index {441}, {773} and {331} facets.