Unusual crystal structure of 12CaO·7Al2O3 is composed by a framework of positively charged nanocages, which enable accommodation of various negative ions (and even electrons) inside these cages. Different filling of cages leads to significant changes in electronic structure and as the result in luminescence properties, as well. Luminescence was studied using time-resolved spectroscopy in VUV in the temperature range from 6 to 300K. Electron loaded samples exhibit UV luminescence band peaked at ∼5eV. The excitation spectrum of this emission has the onset at the energy gap value of 6.8eV, and its decay is well described with the sum of two exponential functions with life-times of τ1=3.7 ns and τ2=29 ns, respectively. Its thermal quenching is well approximated by the sum of two Mott-Seitz type curves with the activation energies of 34meV and 70meV. Experimental results indicate that this luminescence is possibly due to radiative decay of two singlet self-trapped exciton states, which hole components are localized on two non-equivalent framework oxygens.