Selective catalytic reduction of nitrogen oxides (NOx) with C3H6 (C3H6‐SCR) was investigated over NiO catalysts supported on different metal‐oxides. A NiAlOx mixed oxide phase was formed over NiO/γ‐Al2O3 catalyst, inducing an immediate interaction between NiOx and AlOx species. Such interaction resulted in a charge transfer from Ni to Al site and the formation of Ni species in high oxidation state. In comparison to other NiO‐loaded catalysts, NiO/γ‐Al2O3 catalyst exhibited the highest NOx conversion at temperature higher than 450 °C, but a poor C3H6 oxidation activity due to the decreased nucleophilicity for surface oxygen species. By temperature‐programed NO oxidation, it is indicated that nitrate species were rapidly formed and stably maintained at high temperature over NiO/γ‐Al2O3 catalyst. In situ transient reactions further verified the Langmuir–Hinshelwood mechanism for C3H6‐SCR, where both gaseous NO and C3H6 were adsorbed and activated on catalyst surface and reacted to generate N2. Due to the strong metal‐support interaction over NiO/γ‐Al2O3 catalyst, both nitrate and CxHyOz intermediates were well preserved to attain high C3H6‐SCR activity. [ABSTRACT FROM AUTHOR]