Sensitized luminescence properties of various alkali halide single crystals of dosimetric importance doped with aliovalent impurities are studied. Single crystals of KCl co-doped with (Ce,Mn), (Ce,Mg) (Ce,Tb) and (Eu,Tb) are grown using the Czochralski technique. The XRD of grown crystals showed good crystalline nature with face-centred cubic KCl structure. Thermally stimulated luminescence (TSL) and optically stimulated luminescence (OSL) characteristics of grown crystals are investigated after subjecting to gamma dose. TSL response of KCl:Eu,Tb and KCl:Ce,Tb showed an enhancement of 6.5 times and 3.5 times, respectively, compared to singly doped KCl:Tb. Co-doping of the divalent activators such as Mn and Mg did not result in enhanced TSL response with rare earth sensitizers. Notwithstanding the low TSL response, KCl:Ce,Mn showed very high OSL response, six times than that of single-doped KCl:Tb and 3.5 times than that of KCl:Ce,Tb and KCl:Eu,Tb. However, KCl:Ce,Mg did not exhibit noticeable OSL intensity enhancement compared to single doping. The high TSL and OSL response is apparently the conclusive evidence of the energy transfer mechanism between dopants, which is confirmed by photoluminescence studies. The dose–response curve of KCl:Ce,Mn that exhibited very high OSL response showed linearity up to 100 Gy, which indicated the material is a good candidate for dosimetric applications. The growth and characterisation of aliovalent impurity-doped KCl single crystals and mechanism of resonance energy transfer between the dopants are discussed in this paper.