We introduce lipopolysaccharide (LPS) molecularly imprinted polymer (MIP) for efficient capturing and analyzing OMVs, enabling a novel approach to bacterial disease diagnosis based on biorecognition materials. LPS, a unique structure of Gram-negative bacteria, acts as a template molecule capable of forming cyclic hydrogen bonds with functional monomers of MIP. And then it can be recognized by MIP. The prepared MIP efficiently captures OMVs from 100 µL of culture broth via specific affinity LPS in less than 40 minutes with a recovery rate of over 95%. Moreover, MIP exhibit good reusability, with almost identical enrichment performance after 5 repeated cycles, contributing to reducing experimental costs in both time and economy. The captured OMVs can be detected using Western blotting with target protein antibodies or in combination with proteomic analysis, providing a proteomic biomarker platform for early bacteria disease diagnosis.