The concept of constitutional supercooling (CS) including the term itself was first described and discussed qualitatively by in order to understand the formation of cellular structures during the solidification of tin, and then quantified by Tiller, Jackson, Rutter, and Chalmers (1953). On that basis, Winegard and Chalmers (1954) further considered 'supercooling and dendritic freezing of alloys' where they described how CS promotes the heterogeneous nucleation of new crystals and the formation of an equiaxed zone. Since then the importance of CS in promoting the formation of equiaxed microstructures in both grain refined and unrefined alloys has been clearly revealed and quantified. This paper describes our current understanding of the role of CS in promoting nucleation and grain formation. It also highlights that CS, on the one hand, develops a nucleation-free zone surrounding each nucleated and growing grain and, on the other hand, protects this grain from readily remelting when temperature fluctuations occur due to convection. Further, due to the importance of the diffusion field that generates CS recent analytical models are evaluated and compared with a numerical model. A comprehensive description of the mechanisms affecting nucleation and grain formation and the prediction of grain size is presented with reference to the influence of the casting conditions applied during the practical casting of an alloy.