High optical quality Li2B4O7 (LTB) single crystals and glassy phases of pure, doped (Cu, Ag) and co-doped with Cu+Ag have been grown by Czochralski crystal pulling and melt quenching techniques respectively. They were characterized through photoluminescence (PL), thermoluminescence (TL), and UV-VIS-NIR transmission measurements. The PL of glass phase shows light yield comparable to that of single crystal. 80-85 % optical transmission in the range 350-800 nm revealed good optical quality of the glasses which is comparable to the single crystals though the glasses have higher cut off wavelength (lower energy). TL glow peaks of Cu doped LTB single crystal at 200 °C and for Cu+Ag co-doped LTB single crystals at around 170°C and 240°C are useful for the dosimetry applications and found to be linear in the range from 1mGy to 1kGy. However, in glasses no TL was observed in spite of a good PL yield. © 2012 American Institute of Physics.