In this paper, based on irreversible thermodynamic theory, the Helmholtz free energy function, was selected to deduce both the master equations and evolution equations of the constitutive model of a NiTi alloy under high strain. The Helmholtz free energy function contains the parameters of the reflecting phase transition and plastic property. The constitutive model for a NiTi alloy was implemented using a semi-implicit stress integration algorithm. Four successive stages can be differentiated and simulated: parent phase elasticity, martensitic phase transition, martensitic elasticity, and dislocation yield. The simulation results are in good agreement with the experimental results.