Hierarchical Engineering for Biopolymer‐based Hydrogels with Tailored Property and Functionality

Abstract Biopolymer‐based hydrogels offer versatility in biomedical engineering due to their abundance, biocompatibility, tailorable properties, and environmental responsiveness. Realizing their full potential requires understanding the molecular‐level design principles that govern their macroscopic behavior. This review analyzes recent advances in the molecular engineering of biopolymer‐based hydrogels, emphasizing innovative network design strategies and processing methods for precise control over material properties and functions. How molecular design influences hydrogel behavior across multiple length scales are explored, focusing on: 1) network design strategies: approaches like double networks, interpenetrating networks, and supramolecular assemblies to tailor mechanical and responsive properties; 2) processing techniques: methods such as Hofmeister effect‐induced chain aggregating, cononsolvency‐based porous structure controlling, and directional freezing‐induced network alignment to achieve hierarchical and anisotropic structures. How these design principles and processing methods influence critical hydrogel properties like mechanical strength, inner mass transportation, and degradation are discussed. The review also covers advanced fabrication techniques that leverage these molecular engineering approaches to create complex, functional hydrogels. By elucidating the relationships between molecular architecture, processing methods, and resulting material properties, this work aims to provide a framework for designing next‐generation biopolymer‐based hydrogels with enhanced performance and functionality across various applications.