Both refluxing reaction under atmospheric pressure and hydrothermal reaction underautogenous water vapor pressure of two kinds of starting slurry with the initial molar ratio Na: Zn: Li: Si=0.7: 5.4: 0.6: 8.0 and 1.4: 5.4: 1.2: 8.0 made from Zn-Si homogeneous precipitates, lithium fluoride and sodium hydroxide successfully have yielded Zn-hectorites containing Zn²⁺ instead of Mg²⁺ in the trioctahedral sheets. Zn-hectorites have expansion of the basal spacing (d₀₀₁) by the treatment with ethylene glycol on powder X-ray diffraction (XRD) patterns, and characterized by Zn-O vibration in the around 660-670cm^-1 on fourier transform infrared spectrometer (FT-IR) spectra, peaks assigned to Zn2p on X-ray photoelectron spectrometer (XPS) spectra and thermal dehydroxylationat lower temperature on thermogravimetry and differential thermal analysis (TG-DTA). It hasalso clarified that Zn-hectorite synthesized by hydrothermal reaction under autogenous water vapor pressure is relatively large massive particles and has a larger CEC, although it has lower MB adsorptive ability compared to a commercial Mg-hectorite as reference.