Czochralski-grown β-Ga2O3 and β-Ga2O3:Si crystals with the free electron concentrations between 2.5·1016 and 4.3·1018 cm−3 have been characterized by means of pulse height and scintillation time profile measurements in order to assess their basic scintillation properties. At room temperature, with increasing free electron concentration in the studied range, the scintillation yields decrease from 8920 to 1930 ph/MeV, while the mean scintillation decay times pare down from 989 to 61 ns. However, when the brightest β-Ga2O3 sample is cooled down below 100 K, its scintillation yield exceeds 20000 ph/MeV. •Czochralski-grown β-Ga2O3 and β-Ga2O3:Si crystals have been characterized.•Scintillation yield and decay times strongly depend on free electron concentration.•Scintillation yield clearly goes up with decreasing temperature towards liquid N2.