The study aims at improving the adsorption performance of montmorillonite for relatively large molecules. The results show that the interlayer spacing of montmorillonite can be further enhanced through the reaction of montmorillonite containing transitional metal cations with phenanthroline to reach over 1.76 nm. It is shown that the two-step synthetic method, by which metal cations are introduced into the interlayer of montmorillonite and then the coordination compounds are in-situ synthesized, has a better effect. In addition, modified montmorillonite shows a fairly good thermal stability up to 40012.