Ionoluminescence (IL) and photoluminescence (PL) of trivalent erbium ions (Er(3+)) in Gd2O3 nanopowder host activated with Bi(3+) ions has been studied in order to establish the link between changes in luminescent spectra and temperature of the sample material. IL measurements have been performed with H2 (+) 100 keV ion beam bombarding the target material for a few seconds, while PL spectra have been collected for temperatures ranging from 20 °C to 700 °C. The PL data was used as a reference in determining the temperature corresponding to IL spectra. The collected data enabled the definition of empirical formula based on the Boltzmann distribution, which allows the temperature to be determined with a maximum sensitivity of 9.7 × 10(-3) °C(-1). The analysis of the Er(3+) energy level structure in terms of tendency of the system to stay in thermal equilibrium, explained different behaviors of the line intensities. This work led to the conclusion that temperature changes during ion excitation can be easily defined with separately collected PL spectra. The final result, which is empirical formula describing dependence of fluorescence intensity ratio on temperature, raises the idea of an application of method in temperature control, during processes like ion implantation and some nuclear applications.