Abstract In large-scale industry, the WGS reaction is the most widely used method for the purification of hydrogen obtained from natural gas. This is a process that hinges on factors such as temperature, pressure, type of catalyst, etc. In this work, copper-based solids were obtained from hydrotalcites, which were characterized through various techniques and evaluated within the WGS reaction at different temperatures. Hydrotalcite-type precursors displayed thermal behaviors that depend on their composition, whereby higher temperatures become necessary for the collapse of the HTLc structure in the solids with higher zinc and aluminum content. The calcination of precursors led to the formation of CuO particles in all the materials, which were more resistant to the reduction processes as the aluminum content augmented. The catalysts were active in the reaction under study with C0.50Z0.25A0.25 being the most active material due to the higher content of metallic copper on the surface. The most effective material in terms of metallic copper content present on the surface was C0.33Z0.33A0.33, in which the occurrence of CuO was not evinced after its use, in addition to displaying the smallest particle size of Cu0 as well as, possibly, the existence of Cu–Zn interactions on the surface.