Ca-Mg-Al hydrotalcite-like compounds (CaMgAl-HTLcs) were synthesized by a hydrothermal method, and characterized by X-ray powder diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR) and differential thermal analysis (DTA) techniques. The effects of the medium pH value, the molar ratio of the raw materials, the reaction temperature and the reaction time on the structure of CaMgAl-HTLcs were studied. The results showed that increasing treatment temperature and reaction time could improve the crystallinity and monodispersity of hydrotalcite-like compound particles. And well-defined CaMgAl-HTLcs could be prepared at a pH value of 10~11 with n(Zn+Mg+Ca):n(Al) =2. The products synthesized were applied to PVC to improve the thermal stability of PVC.