Rh-promoted YZr-supported Ni catalyst (5Ni/YZr) is investigated for DRM and characterized with X-ray diffraction, Raman, infrared spectroscopy, cyclic reduction–oxidation–reduction temperature programmed experiment, thermogravimetry, and transmission electron microscope. Over 5Ni/YZr, some active sites become inactive under the CO2 stream and limit H2 yield to ∼71%. Upon 4 wt% Rh addition over 5Ni/YZr; more than one type of stable active sites (Rh and Ni) generates, moderate basic sites are enhanced, wide ranges of CO2-interacted surface species (especially bidentate CO2-adsorbed species) are grown and graphitic carbon proportion over spent catalyst declines. This resulted in 87.35% H2 yield and 86.73% CO yield up to 420 min. 5Ni4Rh/YZr catalyst maintains ∼80% H2 yield at the end of 27 h of DRM reaction.