Cathodoluminescence in the scanning electron microscope and photoluminescence in a confocal microscope have been used to investigate the luminescence properties of the stable monoclinic a-phase of Bi2O3. Powders of this oxide have been sintered at temperatures of 500 degrees C and 750 degrees C in air or in nitrogen atmospheres. Spectra of the starting powder and of the samples treated at 500 degrees C show luminescence bands at 1.50 eV and 1.95 eV as well as a band at 2.1 eV, more prominent in nitrogen treated samples. Sintering at 750 degrees C leads to quenching of the 1.50 eV infrared emission and the formation of a broad band with emission above 3 eV. The evolution of Raman bands with the sintering treatments has also been investigated. (C) 2012 Elsevier B.V. All rights reserved.