The structure of melts of the system CaO-Al2O3-SiO2 were studied, using x-ray analysis to determine structural factors and the atomic radial distribution function. On a phase diagram the composition used was close to the fields of crystallization of gehlenite and wollastonite. Gehlenite dissociates at a temperature of 1600°C, forming Ca2SiO4, SiO2, Al2O3, and CaSiO3. The main structural elements of the melt of the system at 1600°C are complexes with the structure of the short-range order of wollastonite, gehlenite, dicalcium silicate, corundum, and cristobalite.