Four different techniques (co-precipitation, urea homogeneous precipitation, citrate sol-gel auto-combustion, solid state formate assisted) were used in preparation of a series of Cu/ZnO/Al2O3 catalysts, having a nominal composition: (Cu/Zn)(mol) = 2.5 and (Cu + Zn)/Al-mol = 3. The catalytic materials were investigated by various methods. The activity of the CuZnAl catalysts in the LT-WGS process was compared. The results revealed that the co-precipitation technique and subsequent thermal decomposition provided the Cu/ZnO/Al2O3 catalyst with the higher specific surface area and more advantageous surface morphology. It was shown that co-precipitation of hydroxycarbonate precursors at constant pH and their subsequent thermal treatment provided the most active WGS catalyst compared to other techniques.