Various formulations of Co, Ni and K modified MoS2-based catalysts were synthesized hydrothermally and compared in their catalytic performance in CO2 hydrogenation at 21 bar and 220 °C-330 °C. The products were CO, CH4 and methanol. The addition of K reduced the selectivity to CH4 and moved the maximum of the methanol formation rate to a higher temperature. The materials were characterized by N2 physisorption, temperature programmed oxidation, temperature programmed reduction, and x-ray diffraction spectra (XRD). Under reducing conditions the catalysts were stable until 700 °C and under oxidizing conditions until 300 °C. XRD had shown mainly a MoS2 phase, as well as metal sulfide in the cobalt and nickel promoted catalysts. Different species of Mo and O were observed under reaction conditions by in situ x-ray photoelectron spectroscopy (XPS). When switching from H2 to CO2 + H2 an increase in the amount of oxygen, both lattice oxygen and surface adsorbates, was observed as a consequence of CO2 addition and H2O formation in the reaction. The amount of lattice oxygen correlates with the minor amount of Mo(VI) detected. Increasing reaction temperature and thus conversion led to an increase of the O 1s signals at 533 eV assigned to surface OH, formate and adsorbed H2O. XPS measurements in CO2 + H2 feed showed an effect of K addition on the adsorbate-related O 1s peak, which appeared at lower binding energy (532 eV) and was assigned to carbonates. This may indicate a different reaction mechanism in the presence of the promoter.