Metastable intermolecular composites (MICs) are known for their high energy density, high burn rate, and low diffusion distance, and they have various applications in military and civilian equipment and tasks. However, the introduction of binders, which facilitate shaping, during the processing of MICs for practical applications can lead to a decrease in the energy release rate and an increase in the required ignition energy. Herein, we incorporated graphene nanoplatelets (GNPs), multi-walled carbon nanotubes (MWCNTs), and expandable graphite (EG) into 90- wt% Al/CuO nanothermites stick using simple extrusion-based direct ink writing to improve their overall performance. The high-temperature expansion characteristics and unique structure after expansion caused EG to perform an important role during Al/CuO nanothermites system combustion, which effectively promotes heat transfer and considerably increases the burn rate (81.6%) and pressure rising rate (103.0%). This study demonstrated EG as a low-cost and efficient combustion catalyst for MICs and introduced a simple approach to modulate the energy release rate, combustion pressure and semiconductor bridge (SCB) ignition performance of MICs through incorporation of small amounts of carbon materials.