A novel approach was applied to synthesize B6O using CaB6 and B2O3 powders as reactants. CaB6 and B2O3 were reacted to generate B6O and CaB2O4 at 1573 K, and the by‐product CaB2O4 was removed by acid leaching. It was found that the samples prepared in this work were oxygen deficient (B6Ox, x ≈ .76–.77). The optimal molar ratio of CaB6 to B2O3 was determined to be 3:5, and excess B2O3 could not lead to a change in the value of oxygen occupancy. Scanning electron microscope images showed that regular holes similar to the morphologies of CaB6 particles were exhibited in the final samples, which could be explained by the diffusion of CaB6 during the reaction process.