The CuMn/ZSM-5 (CM/Z), CuMn/Beta (CM/B), and CuMn/SSZ-13 (CM/S) catalyst samples were prepared via an excess impregnation method to investigate the metal-support effect. The results show that the activity at 550 °C for NO direct decomposition follows the order of CM/Z (53.4%) > CM/B (49.2%) > CM/S (7.9%). The good activity and stability of CM/Z are attributed to a strong support effect including forming more active copper sites of the (Cu2+-O2--Cu2+)2+ and (Cu+-□-Cu+)2+ dimers, which have higher redox activity, capacity of oxygen mobility, and NO sorption capability. The competitive adsorption between NO and O2 on the oxygen vacancy of dimers over CM/Z results in the activity decrease from 53.4% to 40.3% at 550 °C after adding 1 vol% O2. The reaction mechanism over CM/Z was discussed based on the in situ DRIFT and isotopic (18O2) experiments. Two NO adsorbs firstly on (Cu+-□-Cu+)2+ to form N2O, and N2O is activated to produce N2, followed by the NO adsorption on (Cu2+-O2--Cu2+)2+ to form nitrite and nitrate species and decomposition to NO and O2.