The effects of Mo, Mn and Zr transitional metals on the catalytic performance of Ru/sepiolite for CO2 methanation were investigated. The results indicated that addition of the transitional metals affected the activity of the Ru/sepiolite remarkably, and the activities of the catalysts were closely associated with the electronic state of the ruthenium surface. The addition of Mo increased the active surface area, the Ru dispersity, the number of active sites, and the resistance to poisoning. According to the Transition State Theory, when Mo is added into the Ru/sepiolite catalyst, the decrease in surface energy is at a cost of an increment in steric hindrance. When T ≤674 K, the energy factor was dominating, and resulted in a decreasing in the ratio of S(CH4)/S(CO). Otherwise, the steric factor dominated the reaction course.