Abstract K2Mg2(SO4)3 samples showed a more intensive ESR signal corresponding to SO− 3 radical than K2SO4 or MgSO4 samples. A decrease of the ESR signal intensity was observed in K2Mg2(SO4)3 samples with the concentration of doping La or Eu, and it was remarkable with Eu doping. In K3Na(SO4)2 samples, the ESR signal intensity increased with the concentration of doped La and had a maximum at about 1 mol% La2(SO4)3, while it decreased with the concentration of Eu doping similarly to the K2Mg2(SO4)3 sample. Thermoluminescence (TL) intensities in K2Mg2(SO4)3 and K3Na(SO4)2 samples increased with the concentration of Eu doping, with maxima at about 1 mol% and 10−2 mol% Eu2(SO4)3, respectively. With La doping, the TL intensity kept a nearly constant value in the K2Mg2(SO4)3 sample and decreased in K3Na(SO4)2 sample. The TL and ESR phenomena in La- or Eu-doped K2SO4, MgSO4 and Na2SO4 samples were also investigated. Both the TL and the ESR behaviors were discussed on the basis of the differences in radius and charge balance between the constituent cations in the matrix and dopant.