Ru/Al2O3 catalysts with various La2O3 contents were synthesized by impregnation method. The catalysts were tested for selective CO oxidation and characterized by X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy with energy-dispersive spectroscopy, and H2 temperature-programmed reduction. The effects of La addition into Ru/Al2O3 catalysts on structure and performance were investigated. Results show that higher CO conversions (>99%) and CO2 selectivity are obtained at 110–170 °C on RuLa/Al2O3. La doping promotes the dispersion of Ru species, thereby enhancing catalytic activity. The analysis reveals that the modification of La2O3 is favorable for the formation of active Ru species with good dispersion and enhanced selective CO oxidation.