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The photoluminescence spectra of MgxCd1−xSe (0.00⩽x⩽0.46) mixed single crystals grown by the chemical transport reaction technique were investigated. We observed an emission band (I2) due to excitons bound to a neutral donor, an emission band (DA) due to donor-acceptor pair recombination with LO-phonon replicas and a self-activated emission band. These emission bands were shifted to higher energy with increasing x. For the crystals with x=0.46, the donor-acceptor emission band was observed at 2.661 eV in the blue region.