A series of hydrotalcite-derived mixed oxides containing Ni/Mg/La/Al and obtained by thermal decomposition, were characterized by XRD, H2-TPR, CO2-TPD, elemental analysis and low temperature nitrogen sorption techniques. The results confirm the formation of periclase-like structured materials. The catalysts containing lanthanum, incorporated by different methods, i.e. co-precipitation, impregnation and ion-exchange, showed outstanding catalytic activity at 300 °C, with CO2 conversions around 36–87% and CH4 selectivity of 98–99%.