Phase diagram of the pseudo-binary system Bi2O3-Cr2O3 has been reconstructed based upon X-ray diffraction measurement and differential thermal analysis. Four intermediate phases have been determined in this system: Bi14CrO24-based solid solution (beta(1), space group 14/m), Bi10Cr2O21 -based high-temperature solid solution (beta(2), orthorhombic symmetry), a new compound Bi2CrO6 (X, monoclinic symmetry) and the stoichiometric compound Bi6Cr2O15 (eta phase, orthorhombic symmetry, space group Ccc2). (C) 2008 Elsevier B.V. All rights reserved.