The effect of Mg codoping on the Eu3+ luminescence in GaN was investigated by photoluminescence measurements. Two notable emission peaks associated with the 5D0→7F2 transition in the Eu3+ ions were governed by Mg codopants, which corresponded to the change of the dominant peak wavelength from 622.3 to 620.3 nm with an increase in Mg concentration. An optimal amount of Mg also led to enhancement of approximately 20 times of the Eu3+ luminescence. These results indicated that the Mg codopants selectively activated the optical site of 620.3 nm emission due to the elimination of nonradiative deexcitation paths from the 5D0 state.