One of the most important stages of the high-purity chalcogenide glasses’ analytical control is the determination of matrix elements’ content with the uncertainty at the levels of 0.1–0.2 mol.%. The content of the macro-components may differ from the composition of the initial charge; therefore, an important task is the macro-composition determination of the final materials. This article describes the development of the technique for determining the matrix elements of high-purity Ge-Se-Te glasses in the range of germanium content from 10 to 35 mol. %, selenium and tellurium content from 20 to 50 mol. % with the expanded uncertainty within 0.01–0.2 mol. % (P = 0.95) using the inductively coupled plasma atomic emission spectrometry (ICP-AES). A simple technique for the preparation of primary calibration solutions from pure elementary Ge, Se and Te is proposed. The correctness of the analysis results is confirmed by comparing the calculated matrix composition of model glass samples, prepared by direct synthesis from high-purity simple substances in the sealed quartz glass ampoule, with the analysis results. The main advantage of the proposed analysis technique is the absence of the need for the reference samples identical to the analyzed material, which is especially important for determination of new materials’ matrix composition. The minimum sample mass for the determination of matrix elements is about 1 mg, which makes it possible to analyze not only bulk glass samples, but also fibers and expensive materials.