Abstract: | Several novel asymmetric ZnO hierarchical structures were synthesized in diethylene glycol (DEG) with different amount of ammonia solution via solvothermal process. The submicron‐rods or nanorods as the building units are distributed on the two sides in an asymmetric manner, resulting in formation of the shiitake‐like or bouquet‐like morphology. A possible formation mechanism was proposed on the basis of the experimental result. The consumption of the precursor could lead to a two‐step nucleation and growth process. The relative content of the [Zn(OH)4]2− and the [Zn(NH3)4]2+ precursors varies with the amount of ammonia solution, which affect the size and morphology of the asymmetric structures. The [Zn(OH)4]2− complex and the [Zn(NH3)4]2+ complex are absorbed on the positive (0001)‐Zn polar surface and the negative (000–1)‐O polar surface respectively, which lead to the alteration of growth rate of these polar surfaces. |