Recent developments in the study of the intercalation of organoammonium ions into smectites are reviewed. The new developments of the applications of the organoammonium exchanged smectites include the selective adsorption of harzardous organic compounds from water, the immobilization of photo and electroactive species to construct novel photo and electrofunctional materials, the complexation with organic polymers for the enhancement of the mechanical properties. The novel controlled properties of smectites achieved by the modification with the adsorption of organoammonium ions open up new opportunities to tailor the properties of the smectite-organic intercalation compounds. The effects of organoammonim ions and the nature of smectites on the properties of the resulting functional intercalation compounds were discussed.