CO-selective methanation (CO-SMET) is an efficient hydrogen-rich (H2-rich) gas purification technology for proton exchange membrane fuel cells. It is vital to develop suitable catalysts with good low-temperature activity for CO-SMET reactions. In this study, RuNi/TiZrx-mixed metal oxide (RuNi/TiZrx-MMO) catalysts with different molar ratios of Zr/Ti, derived from a Zr-promoted NiTi-layered double hydroxide (NiTi-LDH) precursor were successfully prepared using the co-precipitation and wet impregnation methods. The RuNi/TiZr0.2-MMO catalyst possesses higher catalytic performance in a lower temperature window of 180-280 °C, which can reduce the CO concentration to be below 10 ppm. The characterization results obtained from XRD, BET, SEM, TEM, XPS, TPR, and TPD suggest that the addition of ZrO2 increases the surface area of the catalyst, improves the dispersion of metallic nanoparticles, increases the reducibility of Ni species on the RuNi/TiZr0.2-MMO catalyst's surface, and enhances the adsorption and activation ability of CO, resulting in remarkable catalytic performance at lower reaction temperatures. Moreover, the RuNi/TiZr0.2-MMO catalyst demonstrated long-term catalytic stability and carbon resistance.