In order to study the characteristics of electrothermal plasma interaction with energetic materials, especially the ignition ability, a novel model considering polyethylene and copper ablation is developed, and an ignition experiment system is set up. The parameters of the plasma and the surface conditions of the energetic materials are measured in the testing. The results show the measured first peak pressure to be ~2.2 MPa, the second peak pressure to be ~3.9 MPa, and the visible flame velocity to be ~2000 m s −1 . Circular pits of the order of microns and nanometers in size are observed on the surface of the energetic materials. Further, the parameters of the plasma, including static pressure, total pressure, density, temperature, velocity, copper concentration and PE concentration, are calculated and analyzed by the established model, under discharge currents of 9 kA. The simulation is similar to those of experimental results. A shock wave is observed in the experiment and is presented in the calculations; it plays an important role in the performance of the plasma in the nozzle region, where the parameters of the plasma variation trends are very complex. With the aim of obtaining the overall performance of the plasma, the coupling characteristics of multiple parameters must be taken into account, in accordance with the developed electrothermal plasma model.