The hot compression tests of medium carbon V and V–Ti microalloyed steels are carried out at the temperature of 900–1100 °C and strain rate of 0.01–10 s−1. Three physical constitutive models based on creep theory are studied, the prediction accuracy is compared and analyzed by employing the correlation coefficient (R) and average absolute relative error (AARE), and the deformation/diffusion mechanisms are discussed. The results show that Ti has obvious hardening effect in V microalloyed steel and retards the onset of dynamic recrystallization. The physical constitutive model containing the theoretical value of creep exponent 5 can accurately describe the hot flow behavior of both steels, the prediction accuracy of which is comparable to that of the model containing exponent n, reflecting that the dominant deformation mechanism of both steels is dislocation climbing. Furthermore, a modified physical constitutive model combining diffusion mechanisms of lattice diffusion and grain boundary diffusion shows higher accuracy (R = 0.996, AARE = 3.81% of V steel and R = 0.994, AARE = 4.52% of V–Ti steel), indicating that the diffusion mechanism is controlled not only by lattice diffusion but also by grain boundary diffusion.