• M x WO y -rGO/Al nanothermites were fabricated by in situ and self-assembly methods. • The M x WO y -rGO/Al nanothermites present a dense layer stacked structure. • The energy release of the nanothermites can reach about 3000 J·g −1 . • The nanothermites present outstanding combustion and catalytic performance. The development of nanothermites with high energy release rate is an important direction to the combustion catalysts in solid propellants. Herein, the bimetallic composite oxides (MgWO 4 , CoWO 4 and Bi 2 WO 6 ) were compounded with GO through an in situ solvothermal method, followed by self-assembly with Al nanoparticles in an organic solvent to obtain a new type of nanothermites. The structure, heat release and ignition performance of MgWO 4 -rGO/Al, CoWO 4 -rGO/Al and Bi 2 WO 6 -rGO/Al and their catalytic performances on several energetic materials were investigated. All prepared samples present a dense layer stacked structure. The heat outputs of MgWO 4 -rGO/Al, CoWO 4 -rGO/Al and Bi 2 WO 6 -rGO/Al nanothermites reach 2763.8, 3094.1 and 2853.6 J·g −1 respectively, which are significantly larger than those of Al/CuO (2070.0 J·g −1 ), Al/Fe 2 O 3 (2088.0 J·g −1 ), GO/Al/Bi 2 O 3 (1421.0 ± 12.0 J·g −1 ) and M x WO y /Al without GO. The enhanced performance may be ascribed to the unique structure of bimetallic composite oxides and GO, and uniform compact structure of nanothermites. CoWO 4 -rGO/Al exhibits a higher combustion heat release (3094.1 J·g −1 ), shorter ignition delay time (11.0 ms) and burning time (50.0 ± 2.0 ms), the minimum time of reaching the maximum flame area (20.0 ± 2.0 ms) and the maximum flame propagation speed (7.3 ± 0.7 m·s −1 ), demonstrating outstanding exothermic and combustion properties. The DSC results show that MgWO 4 -rGO/Al, CoWO 4 -rGO/Al and Bi 2 WO 6 -rGO/Al nanothermites reduce the peak temperature of AP (406.5 °C) by 23.8, 62.2 and 25.5 °C, and RDX by 3.2, 4.5 and 3.3 °C, respectively. This study will provide a new strategy of combustion catalysts utilizing the synergistic effects of energization and nanometerization.