In this work a series of [Zn1−xAlx(OH)2](CO3)x/2·mH2O; x=0.25−0.66 were prepared at constant pH in order to study the effect of the thermal treatment on their crystalline srtucture. It was found that is possible to obtain pure Zn-Al hydrotalcite materials within a x = 0.25−0.50 range in comparison with Mg-Al hydrotalcites which yield pure phases in more restricted x ranges (0.25−0.33). All Zn-Al hydrotalcites lost their layered structure at temperatures above 473 K being less stable than their parental Mg-Al hydotalcite (623 K). Specific surface areas of these materials depended strongly on the Zn/Al ratio and calcination temperature, ranging from 280 to 20 m2/g. ZnO and ZnAl2O4 compounds were detected as the calcination products at temperatures higher than 873 K.