In this study, the thermoluminescence (TL) characteristics of Ag‐doped and undoped lithium tetraborate (Li2B4O7, LTB) materials, grown using the Czochralski method, were reported. The TL properties of LTB:Ag, such as glow curve structure, dose response, fading and reproducibility, were investigated. The glow curve of the Li2B4O7:Ag single crystal consists of four peaks located at approximately 75, 130, 190 and 275°C; in undoped LTB, the single crystal shows a broad glow curve with peaks at 65, 90, 125, 160 and 190°C using a heating rate of 5°C/s in the 50–350°C temperature region. The high temperature peak of Ag‐doped sample at 275°C has a nonlinear dose response within the range from 33 mGy to 9 Gy. There is a linear response in the range of 33–800 mGy; after which, a sublinear region appears up to 9 Gy for Ag‐doped LTB single crystal. For undoped single crystal, the dose response is supralinear for low doses and linear for the region between 1 and 9 Gy. The thermal fading ratio of the undoped material is almost 60% for the high temperature peak after 7 days. Ag‐doped LTB single crystal exhibits different behaviour over a period of 7 days.