In this study, a novel, surface-imprinted polymer (MIL-101@MIP) was successfully synthesized using the metal-organic framework MIL-101(Cr) with a large specific surface area as a carrier, which achieved rapid and selective removal of bisphenol S (BPS) from environmental samples. The structure and morphology of MIL-101@MIP were characterized using SEM, XPS, FTIR, TGA, BET, and XRD techniques. The results show that MIL-101@MIP has rough surface morphology and good thermal stability. The large specific surface area (1251.6 m2 g-1) of MIL-101@MIP provides more imprinting sites in MIL-101@MIP; thus, the maximum adsorption capacity of BPS reached 87.76mgg-1 with good imprinting factor 2.08, and equilibrium was achieved in only 10min. Moreover, the process of BPS adsorption onto MIL-101@MIP followed the pseudo-second-order kinetics and Langmuir isothermal adsorption models. In addition, the MIL-101@MIP was utilized as an adsorbent for a solid phase extraction column to determine BPS in seven environmental samples using HPLC, achieving recovery of 89.20–105.78%. The developed MIL-101@MIP is a promising and efficient adsorbent for rapid and selective removal of BPS from the environment.