Site-selective growth on non-spherical seeds provides an indispensable route to hierarchical complex nanostructures that are interesting for diverse applications.H owever,t his has only been achieved through epitaxial growth, which is restricted to crystalline materials with similar crystal structures and physicochemical properties.Anon-epitaxial growth strategy is reported for hierarchical nanostructures, where site-selective growth is controlled by the curvature of non-spherical seeds.T his strategy is effective for site-selective growth of silica nanorods from non-spherical seeds of different shapes and materials,such as a-Fe 2 O 3 ,NaYF 4 ,and ZnO.This growth strategy is not limited by the stringent requirements of epitaxy and is thus av ersatile general method suitable for the preparation of hierarchical nanostructures with controlled morphologies and compositions to open up av erity of applications in self-assembly,nanorobotics,catalysis,electronics,and biotechnology.The interest in the preparation of well-defined hierarchical nanostructures with increasing structural and compositional complexity is driven by their wide applications in selfassembly,e lectronics,p hotonics,c atalysis,a nd biotechnology. [1] During the past decades,the majority of hierarchical complex nanostructures,f or example,t etrapods,o ctapods, branched or tree-shaped nanowires,a nd one-dimensional (1D)/two-dimensional (2D) heterostructures,h ave been syn-thesized through seeded epitaxial growth methods. [2] For example,Zhang et al. reported the growth of hierarchical 1D/ 2D nanostructures through epitaxial growth of CdS and CdSe nanorods on selective facets of hexagonal-shaped semiconductor nanoplates. [3] However, owing to the demand of epitaxy,e pitaxial growth methods are restricted to the growth of hierarchical complex nanostructures consisting of crystalline materials. [4] Moreover,t he growing material and the seed should have almost identical crystal structures and, in most cases,similar physiochemical properties.T othis end, it is necessary to develop non-epitaxial growth routes that are potentially suitable for growing hierarchical hybrid nanostructures consisting of materials with different physicochemical properties.Forthe sake of structural complexity and anisotropy,nonspherical seeds are preferred for the growth of three-dimensional (3D) hierarchical nanostructures.I ntuitively,c ontrolled anisotropic growth of secondary nanostructures from selective areas on the surface of non-spherical seeds could provide an indispensable route to hierarchical nanostructures with greatly increased structural complexity.S ite-selective growth from specific exposed facets can be easily achieved during epitaxial growth, for example by tuning the growth direction. Fornon-epitaxial growth, ageneral mechanism for controlling the growth sites on non-spherical seeds with different morphologies and materials has not yet been discovered. Site-selective non-epitaxial growth on non-spherical seeds has met with very limited success only for seeds w...