A series of ZnB2O4 phosphors doped with different concentrations of Eu and Dy (0.05 0.1, 0.2, 0.5, 1.0 mol%) and co‐doped with Ce (1, 2, 5, 7, 10 mol%) respectively was prepared via the solid‐state reaction technique and the thermoluminescence (TL) behaviour of gamma ray‐irradiated samples was studied. The synthesized samples were irradiated with γ‐rays for the dose range 0.03–1.20 kGy. The TL intensity variations with dose, dopant concentration, and the effect of co‐doping were studied. The TL response curves for ZnB2O4:Eu3+ and ZnB2O4:Dy3+, ZnB2O4:Eu3,Ce3+ and ZnB2O4:Dy3+,Ce3+ phosphor were observed. It was revealed that ZnB2O4:Eu3+ showed a linear TL behaviour for the dose 0.03–1.20 kGy and ZnB2O4:Dy3+ showed linearity for the gamma dose range 0.03–0.10 kGy. Furthermore, fading for all the samples was observed to be less than 10% for a storage period of 30 days. In addition to this, the trapping parameters, especially activation energies were evaluated using the Ilich method and the initial rise method. The activation energy values obtained from both methods were in complete agreement with each other.