Abstract This work reports the thermoluminescence characterization of newly synthesized Li2B4O7 (LTB) and LTB:Cu materials of single crystal and glassy structure. The following basic properties were investigated: glow curve, dose response, fading, reproducibility and batch uniformity. The Cu doped samples and the non-doped single crystal gave TL response, while the non-doped glassy LTB did not up to 10kGy. LTB:Cu single crystals showed promising properties. Their glow curve consists of two well separated peaks (at 165°C and 270°C) in the 50–350°C temperature region. The sensitivity of this material is about 5 times higher than that of the TLD-100. The most attractive feature of these LTB:Cu single crystals is their linear dose response in a very wide range: from 0.3mGy to 10kGy. Unfortunately this material is sensitive to light; the fading of irradiated samples is very quick in daylight, but at room temperature and kept in dark the fading of the 270°C peak is less than 6%.