The synthesis of a composite material with a hierarchical porous structure based on the metalorganic framework MIL-100 and a natural silica material diatomite is proposed in the present study. The structure of the synthesized materials was characterized by a complex of physical-chemical methods (lowtemperature sorption of nitrogen, XRD, TG-DSC). The hierarchical porous structure of the composite was confirmed by the low-temperature nitrogen adsorption method. MIL-100(Fe) and diatomite phases (amorphous silica and quartz) were confirmed by XRD method. The composite structure is stable up to 300 C (confirmed by TG-DSC). The sorption properties of the composite were tested in the removal of toluene vapor. The MIL-100(Fe)/diatomite composite exhibited the high adsorption capacity for toluene (183 mg/g).