Abstract: | We present a facile, spontaneous, and surfactant‐free method to controllably self‐assemble aluminum and bismuth trioxide nanoparticles through the introduction of graphene oxide as a self‐assembly directing agent. The self‐assembled nanocomposites demonstrate significant combustion performance improvements in comparison to randomly mixed aluminum and bismuth trioxide nanoparticles with enhanced pressure generation from 60 to 200 MPa, pressurization rate from 3 to 16 MPa μs−1, burning rate from 1.15 to 1.55 km s−1, and specific impulse from 41 to 71 s. The sensitivity of the self‐assembled aluminum and bismuth trioxide to electrostatic discharge was reduced by four orders of magnitude, without decreasing the combustion performance. Graphene oxide directed self‐assembly can be used to synthesize nanocomposites with diverse combustion properties and controlled ignition sensitivity, which lays the foundation for preparing multi‐functional, highly‐reactive, combustion systems in the future. |