MIL53(Al)-SiO2@Fe3O4 composite was prepared by co-precipitation route with a typical Stober synthetic process and ultrasonic-agitation, then subsequently utilized as a multi-component novel sorbent in solid-phase microextraction (SPME) of aflatoxin B1 in winter herbal teas. Microstructural properties of MIL53(Al)-SiO2@Fe3O4 composite was characterized by using Fourier transform infrared (FTIR) spectroscopy, powder X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) methods, and Brunauer-Emmett-Teller (BET) surface area measurement. The MIL53(Al)-SiO2@Fe3O4 composite was found to be a very effective sorbent in spectrofluorimetric determination of aflatoxin B1 (AFB1) in winter herbal teas via magnetic solid-phase extraction (SPE) route. The proposed method showed a wide linear range from 0.5 to 150 ng/ml, low limit of detection (LOD = 0.5 ng/ml), and an acceptable recovery values (70.7-96.5%) in real samples analysis. This study shows that the suggested method possesses an important potential to use for detecting AFB1 in quality control laboratories.