Luminescence emission from rare earth (REE) ions doped materials are being of interest since can be employed as scintillators, catalysts, battery and magnetic materials, etc. We herein report on the preliminary results obtained from the cathodoluminescence (CL) properties of undoped LaAlO3 (LAO) and LaAlO3: REE3+ (REE=Dy3+, Pr3+ and Eu3+) samples synthesized by a sol-gel process based on the Pechini's method with a spray-drying technique. The samples, previously characterized by means of Environmental Scanning Electron Microscopy and Energy Dispersive X-Ray Analysis Spectrometry, display CL spectra with well-defined peaks that could specifically be associated with the LAO structure (in the range of 300–450nm) and point defects (from 450 to 800nm) spectral regions. The observed wavebands are as follows: (i) 480 and 570 from the Dy-doped LAO correspond respectively to 4F9/2→6H15/2 and 4F9/2→6H13/2 transitions, (ii) 490–638 from the Pr-doped LAO is linked to 3P0→3H4, 1D2→3H4 transitions and (iii) 590 and 620 where the dopant Eu3+ gives rise to 5D0→7F1 and 5D0→7F2 transitions and (iv) a UV-blue broad band is associated with NBHOC in undoped LAO. Such emissions are due to the presence of the 4f electrons of rare earth ions that are shielded by the outer 5s and 5p electrons, the intra-4f emission spectra of REE that induce sharp and narrow wavebands.