Zanthoxyli Radix, the dried root of Zanthozylum nitidum (Roxb.) DC, one of traditional Chinese medicines (TCMs), exhibits various pharmacological activities such as anti-bacterial, anti-inflammatory, anti-tumor, analgesic activity. A sustainable vortex-enhanced magnetic solid phase extraction (VE-MSPE) method combined with ultra-high performance liquid chromatography (UHPLC) was established to enrich and analyze the bioactive quaternary ammonium alkaloids (QAAs) of Zanthoxyli Radix. Fe(3)O(4)@C@CMCS magnetic nanoparticles (MNPs) was first synthesized for selectively adsorbing target QAAs (magnolinine, sanguinarine, nitidine chloride and chelerythrine), which possess excellent adsorption performance after being reused 10 times. The results revealed that the great adsorption rate of Fe(3)O(4)@C@CMCS MNPs for the four QAAs could reach 55.1-78.7 %. In addition, a reliable linear relationship (r >/= 0.9995) and good recovery (97.5-104 %) was obtained. Consequently, the VE-MSPE method applying Fe(3)O(4)@C@CMCS MNPs as a sustainable adsorbent exhibited great potential in the selective enrichment of QAAs in TCM. CI - Copyright (c) 2023 Elsevier B.V. All rights reserved.