Just Accepted Articles have been posted online after technical editing and typesetting for immediate view. The final edited version with page numbers will appear in the Current Issue soon.
Crystalline porous organic frameworks (CPOFs), with their highly ordered pores and tunable organic structures, have shown immense promise as platforms for enzyme immobilization. However, research on enzyme@CPOF composites, particularly for biomedical applications, is still in its early stages and lacks comprehensive and systematic review. This article provides a thorough overview of recent advances in the rational design, synthesis, and application of enzyme@CPOF biocomposites. Emphasis is placed on immobilization strategies and the structure-performance relationships revealed through molecular-level investigations. Furthermore, we highlight emerging applications in biocatalysis and biomedical engineering, and discuss persistent challenges and future directions to advance CPOFs as versatile, high-performance substrates for enzyme immobilization.