The MgGa2O4 ceramics co-doped with Mn2+ and Eu3+ ions were synthesized via a high-temperature solid-state reaction technique. The samples with various Eu3+ concentrations were characterised using high-resolution photoluminescence (PL) spectroscopy. The PL spectra show weak matrix emission in a blue spectral region with dominant excitation band around 380 nm. Manganese ions are highly excited deeply in UV region and exhibit emission band peaked at 502 nm. The Eu3+ ions show characteristic f-f excitation and emission lines. The energy transfer between host defects and activator ions was observed. Luminescence decay curves of Mn2+ and Eu3+ emission showed complex kinetics with both Eu3+-ion concentration and excitation wavelength changes.