Coal is expected to continue dominating the global energy landscape for a considerable period in the future. However, the depletion of high-quality coal resources and the increasing proportion of difficult-to-float coals are exacerbating environmental issues and leading to significant waste of carbon resources, making the clean and efficient utilization of such coals imperative. Enhancing the quality of coal through flotation is a prerequisite for the resource utilization of coal. Difficult-to-float coal, characterized by high hydrophilicity, complex pore structures, and fine particle size, poses challenges for efficient flotation using conventional collectors. Emulsions, owing to their exceptional surface and interfacial regulation capabilities and environmental adaptability, have been employed as flotation collectors for various minerals and have garnered significant attention in recent years for their application in the flotation of difficult-to-float coals. In the pursuit of green and cost-effective flotation technologies for such coals, this paper systematically reviews the causes of poor floatability in difficult-to-float coals and their latest research progress by emulsion flotation. It summarizes the impact of emulsion types and preparation methods on their properties and application areas, with a particular focus on the key mechanisms by which emulsion collectors enhance the flotation of difficult-to-float coals, including surface charge regulation, surface hydrophobicity modification, and interfacial tension control. Finally, this paper outlines future research directions on emulsion flotation, which will likely focus on the precise control of emulsion structure and size, the targeted separation of organic components by emulsion collectors under complex conditions, the development of low-cost and highly biocompatible synthetic reagents, and the development of efficient emulsion storage and transportation equipment.