A series of NiMnTi mixed metal oxides (Ni/Mn‐TiO2, Mn/NiTi‐LDO and TiO2/NiMn‐LDO, NiMnTi‐LDO) were synthesized via different assembling methods and evaluated in the selective catalytic reduction of NOx with NH3(NH3‐SCR). As the results presented, catalysts via diverse assembling methods of LDHs templates afforded different catalytic denitrification (DeNOx) performance, which might be related to the exposure degree of active constituents and the interaction intensity between metal components. Noticeably, compared with Ni/Mn‐TiO2, Mn/NiTi‐LDO and TiO2/NiMn‐LDO catalysts, the NiMnTi‐LDO catalyst deriving from one step in‐situ method NiMnTi‐LDH precursor template exhibited the most desirable performance at temperature window of 150–360 °C in NH3‐SCR (above 90% NOx conversion with 95% N2 selectivity). The specific structure and property of samples were correlated by means of a series of characterizations, where the results indicated that NiMnTi‐LDO possessed the highest surface area, the strongest redox ability, the most abundant acid amount and the best dispersion.