The present research is designed to analyze the effect of different calcination temperature on the structural property, the redox ability and the catalytic behavior of LaCu0.25Co0.75O3 samples in NO + CO reaction. The appropriate elevation of calcination temperature visibly enhances the catalytic behavior of LaCu0.25Co0.75O3 samples, conforming to the sequence: LaCu0.25Co0.75O3-750 > LaCu0.25Co0.75O3-500 > LaCu0.25Co0.75O3-250 > LaCu0.25Co0.75O3-1000. The greatest catalytic behavior is gathered on LaCu0.25Co0.75O3-750 sample at 350 degrees C, with 97% N-2 selectivity and 100% conversion for reactants. At the same time, LaCu0.25Co0.75O3-750 sample shows the superior continuous catalysis resistance. The ratio of Cu+/(Cu+ +Cu2+) and Co2+/(Co2+ + Co3+), the reducing ability and quantity of oxygen deficiencies are regarded as the key points for the enhancement of catalytic behavior. Besides, giving the example of LaCu0.25Co0.75O3-750, all the catalytic steps are provided to deeply explore the catalytic mechanism.