Cyclic penta-twinned noble metal nanocrystals exhibit promising properties due to their unique geometric and electronic structures. However, the controlled synthesis of cyclic penta-twinned nanostructures, especially of noble metals with a high cohesive energy (e.g., Rh), is very difficult, and the corresponding growth mechanism is not fully understood. Herein, we report a facile one-pot hydrothermal approach for the synthesis of cyclic penta-twinned Rh icosahedral nanocrystals. It was found that apart from regulating the surface free energy by changing the concentration or category of the capping agents, the solvent might influence the adsorption ability of the surfactant on the Rh crystal surface, which results in a change in the surface free energy and thus allows the formation of Rh cyclic penta-twinned nanostructures. In addition, due to their unique electronic and geometric structures, the Rh icosahedral nanocrystals exhibit superior catalytic activity and stability for the electrooxidation of ethanol as compared to single-crystal Rh tetrahedral nanocrystals and commercial Rh black.