Silylated layered double hydroxides (LDHs) were synthesized through a surfactant-free method involving an in situ condensation of silane with the surface hydroxyl group of LDHs during its reconstruction in carbonate solution. X-ray diffraction (XRD) patterns showed the silylation reaction occurred on the external surfaces of LDHs layers. The successful silylation was evidenced by Si-29 cross-polarization magic-angle spinning nuclear magnetic resonance (Si-29 CP/MAS NMR) spectroscopy, attenuated total reflection Fourier transform infrared (ATR FTIR) spectroscopy, and infrared emission spectroscopy (IES). The ribbon shaped crystallites with a "rodlike" aggregation were observed through transmission electron microscopy (TEM) images. The aggregation was explained by the T-2 and T-3 types Of linkage between adjacent silane molecules its indicated ill the Si-29 NMR spectrum. In addition, the silylated products show high thermal stability by maintained Si related bands even when the temperature was increased to 1000 degrees C as observed in IES spectra.