Abstract: Aiming at the electrostatic explosion risk arising from friction electrification during the rubber sleeve cutting and peeling process of propellant grain, a set of real-time electrostatic monitoring system was developed. Dynamic electrostatic monitoring and safety analysis were carried out under variable cutting and demolding process parameters. Furthermore, a surface charge inversion algorithm was adopted to realize a quantitative characterization of charge density distribution on propellant grain surface. The results show that during the cutting process, the electrostatic peak occurs at the moment of rubber sleeve fracture during the cutting process. At a cutting speed of 8 cm/s, the maximum electrostatic potential and charge quantity peak reach 3.5 kV and 35 μC, respectively. After cutting, the maximum electric field strength at the interface between rubber sleeve and propellant grain reaches 2.3 MV/m, which is close to the air breakdown threshold. The influence of rolling speed on static electricity is significantly greater than that of contact pressure. When the rolling speed is approximately doubled, the peak potential increases twofold. The surface charge density distribution obtained by the surface charge inversion algorithm is highly consistent with the potential distribution. The peak value of electrostatic potential is −250 V, corresponding to a peak charge density −2.1 μC/m², verifying the safety of the rubber sleeve peeling process.