The effect of surface synergetic oxygen vacancy constructed by bimetallic metal on CO selective catalytic reduction of NOx (CO-SCR) was investigated by loading Fe and Ni on TiO2. Herein, a series of NixFe1−x/TiO2 was prepared by the wet impregnation method. The microstructures, elemental states, and reactivity of the prepared samples were characterized by XRD, HRTEM, EPR, H2-TPD, CO-TPD, NO-TPD, and XPS. The results show that the synergistic effect between Ni and Fe effectively optimized the dispersion of Fe and constructed abundant Ni-O-Fe bonds. Furthermore, the excellent CO trapping capacity led to an increased number of cNi-□-Fe structures (SSOV), which effectively promotes NO activation at low temperatures. The in situ DRIFT spectra illustrated that N2O intermediate species rapidly transformed into N2-based species at 250 ℃, and the catalyst modified with Ni presented excellent NO conversion and N2 selectivity. The Ni0.2Fe0.8/TiO2 sample demonstrated almost 100% NO conversion, 93% N2 selectivity, and considerable stability with a gas hourly space velocity of 33,000 h-1 at 250 ℃. This work provides a novel way for the design and preparation of a bimetallic NO reduction catalyst to promote the further study of efficient CO-SCR catalysts.