The methanation reaction of CO2 is in discussion to be a sustainable pathway to address future questions arising from limited primary energy feedstock and the accumulation of CO2 in the atmosphere. Therefore, the development of highly active and thermostable catalysts for this reaction is an indispensable matter of research. For this reason, an equimolar NiAlOx), benchmark catalyst (44 wt.% Ni loading) was synthesized and modified by doping with Fe or Mn up to 10 wt.% of promoter by co-precipitation at constant pH 9. Their activity and stability performances in the CO2 methanation reaction were evaluated by comparing the conversion versus temperature characteristics before and after an aging period of 32 h at 500 degrees C. Material characterization studies comprising BET, XRD, in situ IR spectroscopy, XPS, H-2 and CO2 chemisorption, and EPR/FMR contributed to derive structure-activity relationships and to obtain a deeper understanding of the catalytic behavior. Promotion with Mn led to a significant enhancement of the catalytic activity. This is assumed to be caused by a higher density of medium basic sites and an enhanced CO2 adsorption capacity on the activated catalyst related to interactions between Mn oxide species and the mixed oxide phase, in combination with a stabilization of the Ni surface area at moderate Mn loadings, Promotion with Fe increased the thermal stability of the catalyst, which is attributed to the formation of a Ni-Fe alloy during catalyst activation. For both phenomena, the optimum molar Ni to promoter ratio for co-precipitated catalysts was found to be around 5.