Engineering metals undergo many transformations in the course of production, none more critical than those that occur during solidification. This chapter discusses the process of solidification and its effects on the structure and properties of cast metals. It describes the relationship between cooling rate, grain size, grain shape, and phase structures. It explains how the transition from liquid to solid state creates the conditions under which microsegregation occurs, and how it impacts the distribution of alloying elements, carbides, and inclusions. The link between solidification and porosity is also discussed along with its detrimental effect on the mechanical properties of metal castings.