The thermodynamic simulation analysis of carbon monoxide water gas shift in rich hydrogen was researched by using the method of Gibbs free energy minimization with Aspen plus software. For the purpose of purifying trace amount of CO in hydrogen, two raw gas compositions, 1%CO–99%H2 and 1%CO–24%CO2–75%H2, were purposely selected, and the influences of water to gas molar ratio (1–7) and transformation temperature (40–280 °C) were investigated. The results showed similar variation law as compared with the water gas shift of a pure CO gas. When the transformation temperature increased, the chemical equilibrium shifted toward the reverse direction, resulting in decreased CO equilibrium conversion; when the water to gas molar ratio increased, the CO conversion increased. The results also showed that CO2 had great negative effects on CO conversion compared with H2. For the CO/H2 feed gas, it was concluded that it was possible to reduce the 1% CO content to 100 ppm at 120 °C with the use of the best low-temperature catalyst reported in literature. If we want to further reduce the trace amount of CO in hydrogen to 10 ppm, it is necessary to develop ultra-low temperature catalysts that are highly active below 70 °C.