Simultaneously exposure of adsorption sites and shortening the transmission paths of target adsorbate are crucial for developing advanced adsorbents. In this work, an in-situ phase inversion-hydrothermal (PIH) method is reported to achieve the anchoring of nanosized metal organic frameworks (MOFs) at the interface of porous polymeric beads. Especially, ligand of MIL-101 was loaded in polyethersulfone (PES) beads via phase inversion process. Followed by hydrothermal process, nanosized MIL-101 was prepared in confined space and immobilized on the interface of PES Beads. The resultant MIL-101@PES Beads could provide shorter transmission paths and more exposed active sites, which avoid the blockage of pore structure in traditional embedded method. Removal of typical volatile organic compounds (VOCs), i.e., benzene-containing oil-and-gas, was chosen to present the adsorption performance of MIL-101@PES Beads. From the dynamic adsorption results, excellent removal ability and reusability were observed on the adsorbents. Beads-3 obtained under moderate feeding ratio presented superior adsorption capacity (245.56 mg/g for benzene and 228.82 mg/g for n-hexane) in mono-component adsorption with 2.52 times transport kinetics (intraparticle mass transfer coefficient of 2.09 s−1) compared with embedded samples. These results demonstrated that MIL-101@PES Beads with shaped morphology and internal nanosized MOFs could serve as adsorbents in removing oil-and-gas. This work provides a novel protocol for the facile synthesis of shaped nanosized MOFs with enhanced performance for VOCs removal.