Using potassium diperiodatonickelate (Ni (IV)) as an efficient initiator, the graft copolymerization of methyl acrylate (MA) onto organophilic montmorillonite (OMMT) was successfully performed in an alkaline medium. Three grafting parameters were systematically evaluated as functions of the temperature, the initiator concentration, reaction time, pH value, and the ratio of MA to OMMT substrate. The structure of the titled graft copolymers (OMMT‐g‐PMA) were confirmed by Fourier transform infrared spectroscopy (FTIR), X‐ray diffraction (XRD), differential scanning calorimetry (DSC), and thermo‐gravimetric analysis (TGA). It was found that Ni (IV) was a highly efficient initiator for graft copolymerization of the MA onto OMMT, i.e., grafting efficiency is as high as 95% and grafting percentage can be facilely controlled within 700% in this study. In addition, the highest grafting efficiency and grafting percentage were obtained when temperature adopted was over 40°C and pH was about 10.3. A single‐electron‐transfer mechanism was proposed to illustrate the formation of radicals and the initiation reaction. Copyright © 2008 John Wiley & Sons, Ltd.