Abstract: Solidification structure is a key aspect for understanding the mechanical performance of metal alloys, wherein composition and casting parameters considerably influence solidification and determine the unique microstructure of the alloys. By following the principle of free energy minimization, the phase-field method eliminates the need for tracking the solid/liquid phase interface and has greatly accelerated the research and development efforts geared toward optimizing metal solidification microstructures. The recent progress in the application of phase-field simulation to investigate the effect of alloy composition and casting process parameters on the solidification structure of metals is summarized in this review. The effects of several typical elements and process parameters, including carbon, boron, silicon, cooling rate, pulling speed, scanning speed, anisotropy, and gravity, on the solidification structure are discussed. The present work also addresses the future prospects of phase-field simulation and aims to facilitate the widespread applications of phase-field approaches in the simulation of microstructures during solidification.