Carbamazepine　(CBZ)　and　its　metabolite　carbamazepine-10,11-epoxide　(CBZEP)　play　vital　role　in　the　treatment　of　epilepsy.　It　is　of　great　importance　to　develop　a　method　for　rapid　and　sensitive　monitoring　of　CBZ　and　CBZEP　due　to　their　narrow　therapeutic　index.　Herein,　an　imine-linked-based　covalent　organic　framework　was　synthesized　by　using　1,3,5-tris　(4-aminophenyl)　benzene　(TPB)　and　1,3,5-triformylbenzene　(TFB)　(denoted　as　TPB-TFB-COF)，and　applied　as　a　solid-phase　microextraction　(SPME)　probe　for　extracting　CBZ　and　CBZEP.　The　TPB-TFB-COF　showed　large　surface　areas　(371　m2　g−1),　high　regular　porosity　(1.23　nm)　and　extraordinary　stability,　which　rendered　it　an　ideal　adsorbent　for　highly　efficient　enrichment　of　CBZ　and　CBZEP.　Accordingly,　an　attractive　strategy　of　the　combination　of　the　TPB-TFB–COF–based　SPME　probe　and　electrospray　ionization　mass　spectrometry　system　(ESI/MS)　was　proposed　for　rapid　screening　and　sensitive　monitoring　of　CBZ　and　CBZEP.　Under　the　optimized　parameters,　the　developed　method　exhibited　good　linearity　for　CBZ　and　CBZEP　in　the　range　of　4–1000　μg　L−1　with　correlation　coefficient　(r)　no　less　than　0.9953,　and　the　corresponding　limits　of　detection　(LODs)　were　0.4　and　2.5　μg　L−1,　respectively.　Moreover,　high　enrichment　factors　(EFs,　202–351　folds)　and　satisfactory　relative　standard　deviations　(RSDs)　of　one　probe　(3.3–5.1%)　and　probe-to-probe　(4.8–5.6%)　were　obtained.　By　using　the　proposed　method,　sensitive　screening　and　quantitative　evaluation　of　CBZ　and　CBZEP　in　mice　whole　blood　and　tissue　homogenates　were　successfully　achieved,　indicating　the　promising　applicability　of　the　TPB-TFB–COF–SPME-AMIS　as　a　powerful　tool　for　drug　monitoring.　©　2022