In the present work, a series of Cu–Co layered double hydroxide (LDH) nanorods were prepared using a co-precipitation reaction with hydrothermal treatment for the first time. Mixed oxides obtained by calcination of Cu–Co LDHs (Cu–Co CLDHs) were used as new catalysts for promoting thermal decomposition of ammonium perchlorate (AP). The catalytic activities were investigated by differential thermal analysis (DTA). Thermal decomposition temperature of AP was considerably decreased in the presence of Cu–Co CLDHs. Cu–Co CLDHs exhibit higher catalytic activity than the mechanical mixture of CuO and Co 2 O 3 . The catalytic mechanism was also briefly discussed.