Fe-pillared montmorillonite(Fe-MMT) was prepared with Ca-montmorillonite(Ca-MMT), ferrous sulfate as the original materials by calcination. The ultrastructures of prepared Fe-MMT were characterized by SEM, TEM, XRD and TGA. The results showed that the crystallinity decreased after calcination of the prepared Fe-MMT, but the thermal stability intensified. The morphology showed distinct characters, and a fraction of Fe substituted Ca resulted in the increased distribution of Fe, with its contents reaching 5.597% which meant 99.95% of Fe was inserted. The specific surface area for Ca-MMT was 29.86 m2/g, but it was increased to 51.29 m2/g for. Furthermore, the adsorption capacity was assessed, and it reached 95.43 mg/g for Fe-MMT, which was dramatically larger than that of Ca-MMT with a value of 15.00 mg/g. Additionally, it can still adsorb more than 88% of pyrene after 5 cycles of application, with the capacity kept at 0.709 mg/g. The results above indicated that the prepared Fe-MMT could be potentially applied in the removal of organic pollutants.