Novel Ru-based catalysts were prepared by impregnating 2 wt% Ru-3(CO)(12) into rare earth (La, Sm, Ce) and barium doped nano-magnesia (RE-Ba-MgO) supports, which were originally prepared by chemical co-precipitation with ultrasonic treatment. The Ru/RE-Ba-MgO catalyst exhibits higher activity, more than three times of that of conventional Ba-Ru/MgO base on water impregnation. Characterization of this catalyst by various techniques reveals that the chemical and textural properties of nano Ba-MgO supports and formation state of barium in support are key factors responsible for the elevated activity of this catalyst.