Layered copper/zinc hydroxide nitrate (CZL) and nickel/zinc hydroxide nitrate (NZL) was synthesized by co-precipitation methods. The effect of pH and raw material molar ratio on preparation was investigated and discussed. Powder X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), and thermogravimetry and differential thermal analysis (TG-DTA) were used to characterize the structure and thermostability of CZL and NZL. The results showed that the thermostability of NZL was much higher than that of CZL. Furthermore, the sodium dodecyl sulfate (DS) and dodecyl dimethyl carboxylbetaine (DCB) intercalation into the gallery of CZL and NZL were synthesized by co-precipitation and ion-exchanged methods. The results found that NZL-DS with pure phase was obtained by both methods; NZL-DCB was only obtained by ion-exchanged method; CZL-DS with two different structures was obtained by both methods, wherein NO3- cannot be totally substituted by ion-exchanged method. Moreover, DCB intercalation into the gallery of NZL and CZL were not successfully prepared by ion-exchanged method due to weak electrical property of DCB.