A wide variety of organisms in nature have excellent structures, which are far superior to artificial machinery. [1] Inspired by nature, the structural characteristics of biological systems were mimicked to design similar new bionic materials, [2,3] to obtain more reliable, efficient, and intelligent material. [4] Porous structure was a prevalent structure in many organisms in nature, such as leaves, [5] trees, and other plants, whose cell structure enhanced fluid transport and adsorption in plant. Porous structures in the fur of animals [6] could reduce the weight of the fur while insulating the heat to maintain the body temperature. [7] The unique hexagonal structure of honeycomb [8] had maximum space utilization and excellent mechanical properties. The porous structure in the skeleton [9] facilitated cell adhesion and growth. And the hierarchical porous structure with both macropores and micropores were more capable of fast mass transfer, [10][11][12] showing great potential for applications in catalysis, [13] adsorption, [5] lithium-ion batteries, [14] fuel cell, [15] supercapacitor, [15] etc.However, it is challenging to construct biomimetic hierarchical porous materials artificially. Most of the methods traditionally used to fabricate cell structures are selective etching, salt leaching, phase separation, foaming, freeze-drying, ice crystal template method, etc. Huang et al. [16] used thermally induced phase separation-salt leaching to prepare polyamide porous bionic scaffolds. Zhai et al. used physical foaming and bead compression molding process to prepare a variety of polymer porous foams, such as polypropylene, [17] polystyrene, [18] polylactic acid (PLA), [19] polycarbonate, [20] polyetherimide, [21] thermoplastic polyurethane (TPU) [22] foams, etc. Bai et al. prepared bone tissue scaffolds with gradient channel pores through the ice crystal template method, [23] manufactured polar bear fur bionic porous fibers via the freeze-drying technology. [24] Nevertheless, these methods are complicated to operate and face great difficulties in mimicking complex, fine, and layered porous structures.The introduction of 3D printing technology, such as direct ink writing (DIW), [25][26][27] selective laser melting (SLM), [28,29] fused deposition modeling (FDM), [30,31] and digital light processing (DLP) [32,33] has taken the design and construction of bionic structures a step further. Compared with traditional molding methods, 3D printing technology possessed extremely high degree of design freedom. However, 3D printing technology is not only limited by the printable materials, but also its limited resolution do not allow the preparation of microscopic holes. It usually also needs to be combined with conventional technologies to prepare hierarchical porous structures with both macroscopic and microscopic pores. For instance, Song et al. [34] used SLM technology