The findings of this study indicate that Cr-advanced steels exhibit increased corrosion resistance when Ni is incorporated into the alloy. To investigate this phenomenon, the corrosion products and corrosion behavior of chromium-advanced steels with varying Ni contents were evaluated in CO2-saturated NaCl solutions at 90 and 180 °C. The underlying corrosion resistance mechanism can be elucidated from two distinct perspectives. At 90 °C, the addition of Ni into Cr-advanced steels causes the transformation of Fe oxides to NiFe2O4, and it offers superior protection for steel. In addition, the NiFe2O4 phase generated with electronegative properties can enhance the adsorption of Fe2+, thereby promoting the precipitation of FeCO3 crystals. Furthermore, the residual Ni in the inner film continues to serve a pivotal role in the filling of a considerable number of pores and cracks. Upon comprehensive evaluation of the associated costs, the Cr-advanced steel with enhanced corrosion resistance through the incorporation of 1.0 wt.% Ni content provides a potential alternative to a conventional 3Cr steel in a CO2 environment. On the other hand, at 180 °C, the concentrations of Fe2+ and CO32− are significantly higher than the solubility of FeCO3 in initial corrosion, which is conducive to generate a denser nanometer-size FeCO3 layer with a better protectiveness, and thus, the effect of Ni is significantly weakened.