In this article, a highly crystalline porous imine‐based covalent organic framework was synthesized at room temperature and used as solid‐phase extraction (SPE) adsorbent for the purification and enrichment of trace sulfonamides (SAs) from food samples. The structure of the obtained material was characterized and studied in detail. The extraction process was optimized and the final elution was determined by the ultra‐high‐performance liquid chromatography‐quadrupole time of flight mass spectrometry method. Low limits of detection (0.02–0.19 μg/kg) were obtained under optimal conditions, with the recoveries ranging from 70.5% to 105.3% when spiked at different levels. The adsorption process of the material for SAs was fitted by the Langmuir and Freundlich adsorption isotherm model, and the extraction capacity for Nitrofuran metabolites from food samples was also investigated for comparison. The results demonstrated that the framework was a good candidate SPE adsorbent that can be used for the enrichment of drug residues in complex matrix, and the work may provide a systematic study method for the development of porous adsorbents.