PZT‐5H piezoelectric ceramic has been recommended for instrument applications for many years. Their dynamic piezoelectric properties under shock compression are worthy of attention in various applications. In order to study the dynamic piezoelectric characteristics of PZT‐5H under impact compression, the impact compression experiments are carried out about the PZT‐5H samples with different thickness by using SHPB as loading system, the impact pressure and the electrical output measurement systems are designed by the authors. Through the impact experiments, discharge voltage and stress are measured to explore the relationship between the axial dynamic piezoelectric voltage constant and the stress pulse. The results indicate that whether quasi‐static or dynamic, the PZT‐5H has a yield stress of approximately 150 MPa. The axial piezoelectric voltage constant of PZT‐5H under shock compression is not a constant but a function of stress, even in the elastic region. In the elastic region, the relationship between the axial piezoelectric voltage constant and the stress is exponentially distributed, while in the plastic region it is linearly distributed. The plastic deformation of the material under stress causes the axial piezoelectric voltage constant of PZT‐5H to decrease continuously. Due to the ferroelectricity of PZT‐5H, the discharge voltage increases inversely after the stress unloading.