The temperature-dependent luminescence properties of γ-Ga2O3nanoparticles prepared by a precipitation method are investigated under steady-state and pulsed-light excitation. The main photoluminescence (PL) emission at room temperature consists of a single blue band centered around 2.76 eV, which hardly undergoes a blueshift of 0.03 eV when temperature goes down to 4 K. The emission behaves with a positive thermal quenching following an Arrhenius-type curve. The data fitting yields two non-radiative levels affecting the emission band with activation energies of 7 meV and 40 meV. On the other hand, time-resolved PL measurements have also been taken and studied as a function of the temperature. The data analysis has resulted in two lifetimes: one of 3.4 ns and the other of 32 ns at room temperature, which undergo an increase up to 4.5 ns and 65 ns at T = 4 K, respectively. Based on both stationary and dynamic PL results, a model of radiative and non-radiative levels associated with the main emission bands of γ-Ga2O3is suggested. Finally, by using PL excitation measurements, an estimation of the bandgap and its variation with temperature between 4 K and room temperature were obtained and assessed against O’Donnell–Chen’s law. With this variation it has been possible to calculate the average of the phonon energy, resulting in 〈ħω〉 = 10 ± 1 meV.