features of components in these structures can engender a synergistic effect on the physicochemical properties of the entire structure and the outstanding properties of their constitutive building blocks. For example, inspired by the 3D hierarchical structure of the gecko's feet, which enables them to climb various textured surfaces, such as concrete and glass, surfaces with strong adhesion have been widely used. [3,4] In addition, the micro/nanoscale hierarchical structures inspired by the lotus plant, which impart self-cleaning properties, prevent the adhesion of rain on windows, antennas, and solar cells, thereby maintaining their performance in harsh environments. [5] Research on the micro/ nano hierarchical structures has facilitated their applications to chemical sensors, [6] fuel cells, [7] and self-cleaning systems [8] owing to their increased surface areas and roughness. In particular, micro/nano hierarchical structures are suitable for these applications because they bolster the advantages of micro-and nanostructures. Typically, microstructures can be used to adjust mechanical properties such as the hardness and elastic modulus. [9] Nanostructures also exhibit characteristics such as hydrophobicity and increased surface area. [10,11] Well-designed and adjustable micro/nano hierarchical structures can be applied to harvesting systems, such as triboelectric generators and water harvesting devices with high performance through controlled mechanical properties and increased surface area. [12,13] Therefore, it is essential to fabricate well-designed hierarchical structures that can be manufactured by means of a low-cost process for applications in engineering fields.Several methods have been suggested for manufacturing micro/nano hierarchical structures on surfaces, including semiconductor fabrication processes, [14] molding and imprinting, [15] chemical synthesis, [16] and etching. [17] In particular, various methods have been proposed for fine-tuning the geometric features at different levels with high precision. For example, Tian et al. proposed hierarchically ordered structures using an electrohydrodynamic structure formation method based on a prestructured polymer under an applied electric field. [18] Lin et al. proposed superhydrophobic surfaces based on hierarchical structures using two-photon polymerization. [19] These methods are effective for fabricating complex micro/nano hierarchical structures on flexible substrates. However, these Three-dimensional (3D) hierarchical structures have been explored for various applications owing to the synergistic effects of micro-and nanostructures. However, the development of spherical micro/nano hierarchical structures (S-HSs), which can be used as energy/water harvesting systems and sensing devices, remains challenging owing to the trade-off between structural complexity and fabrication difficulty. This paper presents a new strategy for facile, scalable S-HS fabrication using a thermal expansion of microspheres and nanopatterned structures. When a specific tem...