A Hierarchical Hydrogel Impregnation Strategy Enables Brittle‐Failure‐Free 3D‐Printed Bioceramic Scaffolds

3D‐printed bioceramic scaffolds offer great potential for bone tissue engineering (BTE) but their inherent brittleness and reduced mechanical properties at high porosities can easily result in catastrophic fractures. Herein, this study presents a hierarchical hydrogel impregnation strategy, incorporating poly(vinyl alcohol) (PVA) hydrogel into the macro‐ and micropores of bioceramic scaffolds and synergistically reinforcing it via freeze‐casting assisted solution substitution (FASS) in a tannic acid (TA)–glycerol solution. By effectively mitigating catastrophic brittle failures, the hydrogel‐impregnated scaffolds showcase three‐ and 100‐fold enhancement in mechanical energy absorption under compression (5.05 MJ m−3) and three‐point bending (3.82 MJ m−3), respectively. The reinforcement mechanisms are further investigated by experimental and simulation analyses, revealing a multi‐scale synergy of fracture and fragmentation resistance through macro and micro‐scale fiber bridging, and nano and molecular‐scale hydrogel reinforcement. Also, the scaffolds acquire additional antibacterial and drug‐loading capabilities from the hydrogel phase while maintaining favorable cell biocompatibility. Therefore, this study demonstrates a facile yet effective approach for preparing brittle‐failure‐free bioceramic scaffolds with enhanced biological functionalities, showcasing immense potential for BTE applications. A hierarchical hydrogel impregnation strategy is proposed to simultaneously enhance the mechanical and biological properties of bioceramic scaffolds. Herein, poly(vinyl alcohol) hydrogel is impregnated into 3D‐printed hierarchically porous β‐TCP scaffolds and reinforced by freeze‐castingassisted solution substitution in tannic acid–glycerol. The hydrogel‐impregnated scaffolds showed significantly improved mechanical energy absorption with additional antibacterial and drug delivery capabilities, suggesting promising applications in bone tissue engineering.