The effect of Na addition on the performance of Rh/Al2O3 catalyst for NO reduction with CO in the presence of H2O and O-2 was investigated. The reacted catalysts were analyzed by the FTIR technique to identify the products for further investigation on the possible catalytic reaction mechanisms and the reasons behind the H2O poisoning. Experimental results show that the removal efficiency of NO by Rh/Al2O3 catalyst was 63% at 250 degrees C but that decreased as the H2O content increased. Adding Na to modify the Rh/ Al2O3 catalyst significantly enhanced the conversion of NO to 99% at 250-300 degrees C even as the H2O content was 1.6 vol%. The FTIR analyses results reveal that the abundant H2O in the flue gas can compete with NO to adsorb on the surfaces of Rh/Al2O3 and Rh-Na/Al2O3 catalysts and further enhance the formation of NO3 that reacts with H. The effects of H2O on Rh/Al2O3 and Rh-Na/Al2O3 catalysts can be eliminated by increasing the reaction temperature to higher than 300 degrees C. Rh-Na/Al2O3 is a feasible catalyst for NO reduction at such condition with relative high H2O and O-2 contents.