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Covalent organic frameworks (COFs) are rigid, crystalline, and porous solids; while linear polymers (LP) are generally flexible, nonporous, and processable materials that have been used for many practical applications. Therefore, hybridizing the rigid crystalline COFs and flexible LPs could offer COF–LP composite materials with sophisticated architectures and unprecedented properties. Recent studies have shown that incorporating LPs into COFs can greatly improve the properties of COFs for applications in many areas, including ionic conductivity, drug delivery, energy storage, and many others. Linear polymers can not only insert into the pore channels of COFs, but also can graft onto COF particles. Furthermore, they can be used as building blocks to construct polyCOFs, making COF–LP composites diverse in their structures and properties. In this chapter, we highlight the recent development of COF–LP composites, with an emphasis on their synthetic approaches and emerging applications. We also briefly discuss the current challenges and future development of these exciting COF–LP composites.

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