The initial solidification of molten steel in the mold is very important, as it is the origin of the final slab, which associates with the surface defects and determines the final quality of casting slab. In this article, six main topics, including the initial solidification study method, molten steel solidification, mold flux structure, fluid flow, oscillation marks formation, and breakout are reviewed with the purpose to explore the intrinsic mechanism of the complex initial solidification process and its related multi-phase heat transfer phenomena. The results summarized here can provide a foundational understanding of the initial solidification and heat transfer phenomena occurring in the continuous casting mold.