The effect of CuO on the thermal behaviour of Zr/KClO4 primer mixtures was studied by thermoanalytical techniques, and the Bruceton method and its related calculation. It was found that the CuO catalytically promoted the decomposition of Zr/KClO4 primer mixtures and shifted the exothermic peak of DSC curves to lower temperatures. In addition, the Zr/KClO4 primer mixture containing CuO had a significant effect on the firing characteristics of electro-explosive devices.