AbstractThe energy, combustion and combustion residues properties of composite modified double‐base (CMDB)propellants with CL‐20 were compared to those propellants with RDX. The energy characteristic of CL‐20/RDX‐CMDB propellants had also been calculated theoretically based on the principle of minimum free energy. The energy property of propellants with CL‐20 was found to be evidently enhanced in comparison to those propellants containing RDX. The findings on combustion properties revealed that the combustion properties of CL‐20‐CMDB propellants were contrary to the of RDX‐CMDB propellants. With the mass fraction of CL‐20 increasing in the propellants, the burning rates of propellants can be enhanced significantly, but the burning rates of propellants containing RDX decreased. Analysis of the combustion residues for CL‐20/RDX‐CMDB propellants revealed that the C, Cu and Pb elements aggregated on combustion surface, which may be useful for guiding the regulation of combustion performance of high‐performance CMDB propellants containing CL‐20.