Laser-induced breakdown spectroscopy was applied to the quantitative determination of the elemental composition of glass samples containing U and Eu as a surrogate for highly radioactive glass waste. The emission intensities of both major and minor elements in the samples were measured simultaneously in the wavelength range from 200 to 780 nm by using an echelle spectrometer. Calibration curves for the concentration determination were obtained from the emission intensities at 358.488 nm for U I, and 459.403 nm for Eu I. Limits of detection for U and Eu were ~ 150 and ~ 4.2 parts per million, respectively.