To study the plasma plume expansion dynamics of nanosecond laser ablating Al/PTFE, the Al/PTFE propellant was prepared by a molding sintering method and the rapid expansion process of the plasma plume was photographed using fast photography technology. The effects of the proportion of Al, laser energy and ambient pressure on plasma plume expansion dynamics are analyzed. The results show that the plume expansion process of laser ablating Al/PTFE plasma can be divided into three stages and this phenomenon has not been reported in the literature. The Al powder doped in PTFE will block part of the laser transmission into the propellant, thus reducing the laser absorption depth of the propellant. In the case of short pulse laser ablation, the reaction rate between Al and PTFE is optimal when the reductant is slightly higher than the oxidant. As the laser energy increases, the light intensity of the plasma becomes stronger, the plasma size becomes larger and the existence time of plasma becomes longer. In the first stage plume, the plume expands freely at the ambient pressure of 0.005 Pa and the plume expansion distance is linearly related to time, while the shock wave formed at the interface between the plume front and the ambient gas at the ambient pressure of 5 Pa and the expansion can be described by S-T theory.