The behaviour of plain carbon as well as structural steels is qualitatively different at different regimes of strain rates and temperature when they are subjected to hot-working and impact-loading conditions. Ambient temperature and carbon content are the leading factors governing the deformation behaviour and substructural evolution of these steels. This review aims at investigating the mechanical behaviour of structural (or constructional) steels during their strain rate (ranging from very low to very high) as well as hot-working conditions and subsequently establishing the structure–property correlation. Rate-dependent constitutive equations play a significant role in predicting the material response, particularly where the experiments are difficult to perform. In this article, an extensive review is carried out on the merits and limitations of constitutive models which are commonly used to model the deformation behaviour of plain carbon steels.