Toward Model Amphiphilic Polymer Co‐Networks: Linking Architecture to Structure and Properties

Amphiphilic polymer co‐networks (APCNs) are a unique class of soft matter, combining hydrophilic and hydrophobic polymer segments within a permanently connected macromolecular network. This combination gives rise to dual swelling in polar and nonpolar solvents, leading to hierarchical microstructures and tunable physical properties. In this review, we summarize recent advances in the synthesis, architecture, and behavior of APCNs, with a focus on well‐defined model systems that provide quantitative insight into structure–property relationships. Covalent and electrostatic cross‐linking strategies are discussed alongside the resulting morphologies, domain sizes, and swelling‐dependent mechanical properties. Besides bulk properties, interfacial features are also considered. Model APCNs serve as a unifying framework for connecting macromolecular design, mesoscopic structure, and macroscopic behavior, offering a rational basis for designing functional soft materials with tailored swelling, transport, and mechanical characteristics.