We report a facile interfacial assembly strategy for the preparation of flexible polyphenol-based films for antibacterial and antiultraviolet applications. The free-standing films can be instantaneously formed via spraying tannic acid (TA) at the surface of carboxymethyl chitosan (CMCS) solutions. Compared with the traditional castingevaporation procedure on solid substrates, the liquid interfacial assembly method for the construction of free-standing films is rapid and facile, which prevents the interface separation procedure from the substrates. The thickness and mechanical properties of the films are well controlled by changing the incubation time. The low-field nuclear magnetic resonance was used to analyze the water distributions inside the films and to distinguish the cross-linked structure of CMCS−TA films with different thicknesses, revealing the dynamics of the film formation process. Importantly, the films exhibit outstanding antibacterial and antiultraviolet properties, which are promising in the applications of wound dressings. This study provides a new avenue for the assembly of flexible free-standing films with multifunctionality via a facile and low-cost fabrication process.