A series of NiFe mixed oxide catalysts were prepared via calcining hydrotalcite-like precursors for the selective catalytic reduction of nitrogen oxides (NOx) with NH3 (NH3-SCR). Multiple characterizations revealed that catalytic performance was highly dependent on the phase composition, which was vulnerable to the calcination temperature. The MOx phase (M = Ni or Fe) formed at a lower calcination temperature would induce more favorable contents of Fe2+ and Ni3+ and as a result contribute to the better redox capacity and low-temperature activity. In comparison, NiFe2O4 phase emerged at a higher calcination temperature, which was expected to generate more Fe species on the surface and lead to a stable structure, better high-temperature activity, preferable SO2 resistance, and catalytic stability. The optimum NiFe-500 catalyst incorporated the above virtues and afforded excellent denitration (DeNOx) activity (over 85% NOx conversion with nearly 98% N2 selectivity in the region of 210–360 °C), superior SO2 resistance, and catalytic stability.