Controlling the surface chemical and physical properties of materials and modulating the interfacial behaviors of biological entities, e.g., cells and biomolecules, are central tasks in the study of biomaterials. In this context, smart polymer interface materials have recently attracted much interest in biorelated applications and have broad prospects due to the excellent controllability of their surface properties by external stimuli. Among such materials, poly(N-isopropylacrylamide) and its copolymer films are especially attractive due to their reversible hydrogen-bonding-mediated reversible phase transition, which mimics natural biological processes. This platform is promising for tuning surface properties or to introduce novel biofunctionalities via copolymerization with various functional units and/or combination with other materials. Important progress in this field in recent years is highlighted.