A combined photoconductivity, absorption, and thermoluminescence study was performed to understand the absence of luminescence from Ce3+ in LaAlO3:Ce3+. It is demonstrated that the absence of luminescence is the result of Ce3+ ionization from the 5d excited states, which are all located in the conduction band. Ce3+ ionization is accompanied by the formation of several broad absorption and photoconductivity bands, which are assigned to electron traps. A time and temperature dependent optical investigation of these traps reveals the conditions under which electrons are transferred from Ce3+ to traps and vice versa, from traps back to Ce4+. The observed difference in energy needed to thermally or optically release electrons from traps is qualitatively explained in terms of the location of the ground and excited states of the electron traps with respect to the conduction band.