AbstractNovel metastable intermixed composites (MICs) constructed by carbon nanomaterials are expected to achieve high energy content and high combustion efficiency, but traditional preparation technologies always bring barely improvement in performance. Herein, novel PVDF/CuO/Al@CNTs MICs with independent continuous carbon nanotubes (CNTs) conductive networks were prepared by thoroughly utilizing the conductivity and photothermal properties of CNTs. A conductive network can be constructed at the interface of each encapsulated PVDF/CuO/Al particle with the addition of >0.5 wt% CNTs. The great increase in electrical and thermal conductivity of PVDF/CuO/Al@CNTs MICs indicates excellent energy transfer efficiency across the sample. Significant enhancement of the combustion reaction has been achieved, with the minimum ignition energy and ignition delay time of PVDF/CuO/Al@CNTs3 reduced by ~31% and ~50%, respectively. This indicates that the CNTs with unique photothermal properties can be utilized as an effective igniter. Moreover, the optimal PVDF/CuO/Al@CNTs1 MICs enhanced the pressurization rate (~300%), energy output (~55%), and combustion velocity (~200%). The mechanism of the fast combustion reaction can also be discussed by the weak interface interaction and the energy conductive of the CNTs network throughout the sample. This work provides a modern strategy for strong combustion MICs that can be generalized and applied in the field of energetic materials.Highlights An independent continuous CNTs conductive network was prepared with a small amount of CNTs. The electrical and heat conversion efficiency is greatly improved. CNTs with unique photothermal properties can be utilized as an effective igniter. The laser sensitivity is improved, and the reaction energy, pressure, and pressure rates are significantly increased. The combustion performance was significantly improved, and more intense, and the combustion speed was significantly increased.