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The present paper reports on MnCoFeO4 spinels with peculiar composition and their catalytic behavior in the reactions of complete oxidation of hydrocarbons. The samples were synthesized by solution combustion method with sucrose and citric acid as fuels. All samples were characterized by powder X-ray diffraction, N2-physisorption, scanning electron microscopy, thermal analysis, X-ray photoelectron spectroscopy, and Mössbauer spectroscopy. The catalytic properties of the spinels with Mn:Co:Fe = 1:1:1 composition were studied in reactions of complete oxidation of methane, propane, butane, and propane in the presence of water as model pollutants. Both prepared catalysts are nanosized materials. The slight difference in the compositions, structure, and morphology is due to the type of fuel used in the synthesis reaction. The spinel, prepared with sucrose, shows a higher specific surface area, pore volume, higher amount of small particles fraction, higher thermal stability, and as a result, more exposed active sites on the sample surface that lead to higher catalytic activity in the studied oxidation reactions. After the catalytic tests, both samples do not undergo any substantial phase and morphological changes; thus, they could be applied in low-temperature hydrocarbon oxidation reactions.