Mixed nanopowders of transition alumina prepared by combustion synthesis and phase pure ultra-porous α-alumina by oxidation method were investigated using low temperature time-resolved cathodoluminescence and photoluminescence spectroscopy under VUV-XUV excitation. In all samples along with the 7.6 eV emission of self-trapped excitons of α-alumina, luminescence bands due to F, F+ centres with maxima at 3 and 3.8 eV and other UV–visible luminescence bands of intrinsic and extrinsic origin with varying intensity depending on sample preparation method and thermal treatment were studied. In alumina nanopowders the excitonic excitation peak at ∼9.1 eV near fundamental absorption edge is shifted to the higher energies by 0.15 eV in comparison with the same feature in single crystals. The nanostructure of alumina is responsible for this shift.