This study investigates the influence of cooling rate on the solidification behavior and crystalline phase evolution of equiatomic Ni–Ti alloys using molecular dynamics (MD) simulations. The simulations were conducted by cooling the system from 2000 to 300 K at different rates (0.25 K/ps, 0.75 K/ps, and 2 K/ps). The results reveal that cooling rate plays a critical role in finding the final microstructure. At lowest cooling rate (0.25 K/ps), system exhibits partial formation of the B2 phase with a largely amorphous matrix, indicating limited crystallization due to kinetic constraints. At 0.75 K/ps, the structure remains mostly amorphous with minimal local ordering. At the highest rate (2 K/ps), the alloy shows the emergence of localized FCC and HCP regions, suggesting the onset of crystallization under rapid undercooling. These findings demonstrate that the thermal pathway significantly affects phase selection and microstructural evolution in Ni–Ti alloys, providing insights for tailoring material properties through controlled solidification.