Cucurbit[7]uril‐Based Plug‐and‐Play Platform on Bacterial Surfaces for Constructing Functional Supramolecular Biohybrids

ABSTRACT Integrating bacteria with synthetic materials to construct biohybrid systems is an emerging strategy for developing functional living materials. In contrast to static covalent conjugation, engineering bacterial surfaces with supramolecular approaches offers reversible, modular, and dynamic control. In this study, we developed a robust cucurbit[7]uril‐based supramolecular platform installed on the surface of bacteria, enabling the “plug‐and‐play” construction of functional biohybrids through host–guest interactions. This versatile strategy maintains bacterial integrity while allowing reversible and tunable surface modification. Using this platform, we successfully prepared functional biohybrids for diverse biomedical applications, including fluorescence imaging, drug delivery, and bioorthogonal catalysis, demonstrating its modularity and broad applicability. Notably, tumor‐targeting bacteria equipped with catalytic modules achieved in situ synthesis of proteolysis‐targeting chimeras (PROTACs) within the tumor microenvironment, leading to targeted protein degradation and significant tumor suppression in vivo, highlighting their potential for precision cancer therapy.