Tetrapodal ligand L (2, 2, 2', 2'-tetra[N-benzyl-N-phenyl (acetamide)-2-oxymethyl] n-butyl ether) and complex [TbL] (ClO4)3 are synthesized. The complex ion with tetrapodal ligand L, [TbL]3+ is intercalated into the interlayer space of montmorillonite (MMT) by ion exchanging. The obtained luminescent supramolecular composite material, [TbL]3+-MMT is characterized by elemental analysis, X-ray diffraction, Fourier transform infrared spectroscopy, and ultraviolet-visible spectroseopy. At the same time, the luminescent properties of the material are also studied. The results show that the intercalated material with regular layered structure and the interlayer spacing (d001) approximate to the diameter of the complex ion arranged in the interlayer space of the MMT in the formation of a monolayer emit characteristic green emission of Tb3+ strongly under the excitation of ultraviolet light. It is also found that the relative luminescence intensity, the luminescence monochromatic index and the light stability of the intercalated material are distinctly improved after the [TbL]3+ has been intercalated into the MMT. And the excitation wavelength of the complex is modulated till the red shift occurs in the composite material.