Development and application of solid rockets have put forward new requirements for the combustion performance of AP/HTPB propellants. Herein, carbon-supported Ti/Co bimetallic oxide (MTiCo) nanocomposites with carbon skeleton and porous structure were proposed to use as catalysts for improving the combustion performance of AP/HTPB propellants. For AP decomposition, MTiCo-2 (2.0 wt%) reduced the AP HD temperature by 93.1 oC and enhanced heat release by about 356.3%. Simultaneously, MTiCo-2 (2.0 wt%) significantly decreased Ea of AP HD stage by 51.4%. MTiCo-2 (2.0 wt%) also reduced the ignition delay of AP/HTPB propellant by 78.3% and enhanced combustion rate by 192.0%. The synergistic effect of catalysis and combustion support of MTiCo-2 provided by the structure of carbon-supported Ti/Co bimetallic oxide was the main mechanism for improving the combustion performance of AP/HTPB propellants..