The[Co(naphophen)(PPh 3 )(OH 2 )]ClO 4 and [Co(naphophen)(PBu 3 )(OH 2 )]BF 4 (where naphophen = bis(naphthaldehyde)1,2-phenylenediimine) complexes were synthesi s zed and chracterized by FT-IR, UV-Vis, 1 H NMR, 13 C NMR spectroscopy and elemental analysis techniques. The coordination geometry of the synthezised complexes were determined by X-ray crystallography. Cobalt(III) complexes have six-coordinated pseudo-octahedral geometry in which the O(1), O(2), N(1) and N(2) atoms of the Schiff base forms the equatorial plane. These complexes show a dimeric structure via hydrogen bonding between the phenolate oxygen and the hydrogens of coordinated H 2 O molecule. The theoretical calculations were also performed to optimize the structure of complexes in the gas phase to confirm the structure propose by X-ray crystallography. In addition, UV-Visible and IR spectra of complexes were calculated and compared with the corresponding experimental spectra for more structural confirmation. The obtained complexes were incoporated onto the Montmorillonite-K10 nanoclay via simple ion-exchange reaction. The structure and morphology of the obtained nanohybrids were identified by FT-IR, XRD, TGA/DTA, SEM and TEM techniques. Based on the XRD results of the new nanohybrid materials, the Schiff base complexes were intercalated in the interlayer spaces of clay. SEM and TEM micrographes of the clay/complex shown that the resulting hybrid nanomaterials has layer structures.