Abstract <p>Structure formation in a Fe–Al–C system during high-temperature interaction of a Fe–Al melt with carbon fibers is studied by scanning electron microscopy. The results of microstructure studies show that spherical droplets based on binary carbide Fe₃AlC_<i>x</i> formed as a result of a highly exothermic reaction between carbon and a Fe–Al melt are formed on the surface of carbon fibers. As a result of dendritic liquation, a cellular structure with a cell size of ~200 nm develops inside the droplets. Owing to the segregation of carbon atoms dissolved in a droplet of a Fe–Al melt, a multilayer graphite coating with a thickness of about 5 μm is formed on its surface. The average value of the microhardness of the spherical droplets is ~2500 MPa. The results of the work can be useful in the production of composite materials based on iron aluminides reinforced with carbon fibers.</p>