Impurity doping has yielded a number of useful optical and catalytic alloy nanoparticles, by providing synthetic routes to unprecedented nanostructures. However, Zn is difficult to use as a dopant in alloy nanoparticles due to the difficulty in reduction, and therefore little has been reported on Zn-doped alloy nanoparticles and their potential applications. Herein we report an unusual role of the dopant Zn as a crystal growth modifying agent to cause the formation of novel concave Rh nanostructures, namely nanotents. We could further prepare unprecedented hierarchically stacked Rh nanoframes and dendritic nanostructures derived from them by understanding the role of various surface-stabilizing moieties. We also report the usage of new Rh nanostructures in selective hydrogenation of phthalimides.