Abstract―Compound Cu3NaS2 has been prepared by solid-phase reactions from copper and sodium sulfides Cu2S and Na2S. It has been shown that compound Cu3NaS2 has hexagonal structure with lattice parameters a = 13.9398 ± 23 Å and c = 21.4637 ± 74 Å. After 6 months after synthesis, compound Cu3NaS2 spontaneously transforms at ambient temperature from hexagonal structure into phase with face-centered cubic (FCC) lattice. The dimension of coherent-scattering regions (CSR) for the FCC phase determined from the broadening of diffraction lines varies from ~25 nm at ambient temperature to ~110 nm at 500°C. DSC curves show anomalies at temperatures of 108 and 436°C corresponding to endothermal reversible transitions without change in the type of crystal lattice. The authors consider these anomalies to be due to redistribution of copper and sodium cations over possible crystallographic positions.