Single crystals of Li2B4O7 (LTB) doped with Cu and Ag and Cu, Ag co-doped have been grown using the Czochralski technique. Luminescence studies revealed a sensitizer role of Ag in the LTB:Cu,Ag crystal. It is found that, despite an energy transfer from Ag + to Cu+ centers, emission from both the centers participate in the thermally stimulated luminescence (TSL) of co-doped. We propose that the LTB:Cu,Ag crystal will be a better and efficient material for dosimeters [TSL as well as optically stimulated luminescence (OSL)] compared to singly doped LTB crystals in a photo-readout system having a maximum response in the 200 nm to 600 nm range. © 2013 Elsevier B.V. All Rights Reserved.