The final microstructure and property of metallic materials are determined by hot-working, in terms of phase transformations. With rapid development of the non-equilibrium technology, the processing of hot-working is becoming extreme and versatile, so that the thermodynamics and kinetics controlling the phase transformation is changed from the inter-independence corresponding to brief near-equilibrium process to the highly correlation corresponding to complicated extremely non-equilibrium process. Accordingly, the classical theory, basing on the independent treatment of thermodynamics and kinetics, has become unsuitable to describe the mechanism, predict the microstructure and control the process. This key problem needs to be solved urgently for high-end manufacturing industry, while brings challenges and opportunities for investigations of non-equilibrium phase transformation. The present review is focused on martensitic transition in Fe via Bain path, microstructure regulation by martensitic transformation in low-alloyed steels, and GB migration and the thermal stability of grain growth, quantitatively summarizing the correlation between thermodynamics and kinetics. On this basis, it is aimed to discuss the intrinsic law between thermodynamics and kinetics of phase transition, and thus guide the microstructure design for typical industrial alloys.