Layered double hydroxides are nano-ordered layered compounds. Layered double hydroxide (LDH) well known for its ability to intercalate anionic compounds has been prepared conventionally only with divalent and trivalent cations. In this study, Zn–Si LDH consisting of divalent and tetravalent cations was prepared, and reacted with organic acids and formed nano-hybrid materials. X-Ray diffraction patterns of the prepared LDH (Zn–Si–CO3) showed that interlayer spacing of the LDH was 0.67 nm and increased to be 4.2 nm in the case of stearate anion as the guest. The spacing 0.67 nm was small compared to the usual LDH (Zn–Al–CO3) of 0.76 nm in the case of carbonate anion as the guest. Also, DTA, TG and DTG analyses indicated that the electrostatic force between the layers and carbonate anions increased where the carbonate anions in Zn–Si LDH decomposed at 259 °C while those in Zn–Al–CO3 decomposed at 230–240 °C.