Surface molecularly imprinted polymers (MIL-101@MIPs) were prepared using MIL-101 as supporting core, imprinted polymers as selective shell synthesized with coumarin-3-carboxylic acid as dummy template of Zearalenone (ZEN), methacrylic acid as functional monomer, and ethylene glycol dimethacrylate hydroxyethyl methacrylate as cross-linker. The polymers were characterized by scanning electron microscopy, transmission electron microscopy, energy–dispersive X-ray spectroscopy, X-ray diffraction, and particle-size distribution analyses. MIL-101@MIPs were used as the sorbent to compose the self-made cartridge. The cartridge was used to purify and enrich ZEN from real samples. Under optimized SPE conditions, a self-made cartridge can be reused for at least seven cycles. Elution was monitored with a high-performance liquid chromatography–fluorescence detection system. The linearity of the method ranged within 6.25–250 ng kg−1. The limits of detection ranged within 2.09 – 4.16 ng kg−1, and the limits of quantification ranged within 6.25 –12.50 ng kg−1, respectively. The matrix effects of four real samples were discussed. The spiking recoveries of ZEN ranged within 81.70%–90.10% with relative standard deviations lower than 5.56%. The performance of the self-made cartridge and immunoaffinity column was compared by chromatography.