In this study, the clathrates of fumarate tetracyanonickel dioxane, given by the formula M-2[(fumarate) Ni(CN)(4)]center dot 2(1,4-Dioxane) (M = Co, Ni, Cd and Hg), have been obtained for the first time through chemical methods. These clathrates have been characterized by elemental, thermal, FT-IR, and FT-Raman spectroscopies. The parameters of structures of clathrates have been determined by X-ray powder diffraction. The thermal behaviors of these clathrates have been also investigated by thermo-gravimetric analysis (TGA), differential thermal analysis (DTA), and derivative thermal gravimetric analysis (DTG) in the range of 20-900 degrees C. X-ray powder diffraction data have been recorded at ambient temperature in the 28 range 5-50 degrees. The FT-IR and FT-Raman spectra of clathrates have been recorded in the region of 4000 400 cm(-1) and 4000-100 cm(-1), respectively.