Direct carbon fuel cell (DCFC) is a promising technology with high energy efficiency and abundant fuel. To date, a variety of DCFC configurations have been investigated, with molten hydroxide, molten carbonate or oxides being used as the electrolyte. Recently, there has been particular interest in DCFC with molten carbonate involved. The molten carbonate is either an electrolyte or a catalyst in different cell structures. In this review, we consider carbonate as the clue to discuss the function of carbonate in DCFCs, and start the paper by outlining the developments in terms of molten carbonate (MC)-based DCFC and its electrochemical oxidation processes. Thereafter, the composite electrolyte merging solid carbonate and mixed ionic–electronic conductors (MIEC) are discussed. Hybrid DCFC (HDCFCs ) combining molten carbonate and solid oxide fuel cell (SOFC) are also touched on. The primary function of carbonate (i.e., facilitating ion transfer and expanding the triple-phase boundaries) in these systems, is then discussed in detail. Finally, some issues are identified and a future outlook outlined, including a corrosion attack of cell components, reactions using inorganic salt from fuel ash, and wetting with carbon fuels.