A new approach to preparing a series of Co/Sm2O3 catalysts for hydrogen production by the dry reforming of methane has been developed. The catalyst precursors were synthesized with a simple method, including the evaporation of aqueous solutions of cobalt and samarium nitrates, followed by a short-term calcination of the resulting material. The as-prepared and spent catalysts were characterized using X-ray diffraction, scanning electron microscopy, transmission electron microscopy, temperature-programmed reduction, and thermogravimetric analysis. The content of cobalt in the synthesized materials affects their phase composition and carbonization resistance in the dry reforming of the methane reaction. It has been shown that preheating in N2 atmosphere produces catalysts that provide a stable yield of hydrogen and CO of 94−98% for at least 50 h at 900 °C. These yields are among the highest currently available for the dry reforming of methane catalysts made from Co-Sm complex oxides. It has been established that the decrease in the amount of cobalt in the catalyst and its preheating to an operating temperature of 900 °C in a nitrogen flow help to prevent the carbonization of the catalyst and the sintering of metal particles.