This research deals with the luminescence and physical properties of Gd3(Ga,Al)5O12:Ce single crystal set and it is a complementary study to analogous (Y,Gd)3Al5O12:Ce and (Gd,Lu)3Al5O12:Ce single crystal sets. Those three groups of materials show similar luminescence and physical properties. In this research, the influence of substitution Ga for Al in Gd3(Ga,Al)5O12:Ce single crystals on the luminescence and scintillation characteristics as well as thermodynamical stability of the garnet phase is studied, and it is compared to (Y,Gd)3Al5O12:Ce and (Gd,Lu)3Al5O12:Ce single crystal sets. The unbalanced substitution Ga for Al makes garnet phase thermodynamically unstable and leads to the formation of the multiphase system with luminescence centers in UV and visible spectral ranges. The wavelength-dispersive X-ray spectroscopy, X-ray powder diffraction analysis, photoluminescence and decay kinetic measurements reviled all phase types within multiphase crystals. Temperature dependent measurements were applied to determine the quenching mechanism for Ce3+ luminescence. The timing characteristics are studied as the function of Ga content. •Instability of the garnet phase and formation of the secondary phase inclusions discussed.•Temperature dependence of the decay time of Ce3+ emissions in garnet phase studied.•Energy transfer processes between secondary phase inclusion and target garnet phase discussed.