The graft copolymerization of sodium acrylate (SA) onto organophilic montmorillonites (OMMT) initiated by redox reaction of potassium diperiodatonickelate (IV) [Ni(IV)] with reactive groups on OMMT substrate was studied in alkaline medium. The grafting parameters have been investigated as a function of the ratio of monomer to OMMT, the concentration of initiator, temperature, and pH value. The structure of the graft copolymer (OMMT-g-PSA) was systematically characterized by Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), and scanning electron microscope (SEM). It was found that [Ni(IV)] belongs to a highly efficient initiator for graft copolymerization of SA onto OMMT via the redox iniation (grafting efficiency > 95%). Furthermore, the experimental results also showed that the graft copolymer gels synthesized under optimal condition exhibited a maximum water absorbency of 1104 g/g in distilled water and 111 g/g in 0.2 wt % NaCl solution, respectively, and its water retention ability is more than 91% after centrifugal separation for 2 h. (C) 2008 Wiley Periodicals, Inc.