Understanding the deformation and microstructure evolution characteristics of polycrystalline NiTi under shock compression is of significance and importance for its science insights and engineering applications. In this paper, the shock recovered experiments of Ni₅₂Ti₄₈ by copper momentum trapping were conducted on magnetically driven high velocity flyer plates device CQ-4, and then the method of Electron backscatter diffraction (EBSD) was used to characterize the microstructure evolution characteristics of recovered Ni₅₂Ti₄₈ samples. To unravel the relationships between the plastic deformation and microstructures of shocked Ni₅₂Ti₄₈ samples, molecular dynamics (MD) simulations were performed to simulate and compare the experimental cases. The simulated results show very good agreement with the experimental ones. After shock plastic deformation, high density dislocations, deformation twins (112 type) and new grains are produced in the recovered samples. And no phase transition from austenite to martensite structures is observed, which is consistent with our previous results of shock wave profile experiments. On this basis, the detailed MD simulations were conducted to explore the microstructure evolution regularities and formation mechanisms of Ni₅₂Ti₄₈ at different initial ambient temperatures (300 K, 500 K) and shock loading velocities (0.6 kms⁻¹, 0.8 kms⁻¹ and 1.0 kms⁻¹), which give some new insights into the relationships of shock plastic deformation and microstructure evolution and a reasonable explanation of experimental phenomena.