Abstract <p>Using inductively coupled plasma atomic emission spectrometry and flame atomic absorption spectrometry, methods have been developed for determining the content of Co, Cr, Ti, and V in a wide concentration range (from 1 ×10^–3 to <i>n</i> × 10%) in materials based on tungsten carbide without separating the matrix and using certified solid standard samples. Depending on the chemical, phase, and disperse composition, as well as the method for obtaining compounds based on tungsten carbide that form types of materials with different properties and very different solubility, various sample preparation schemes were used. The analytical parameters for determining Co, Cr, Ti, and V have been found, the operating conditions of spectrometers have been optimized, and the calibration methods have been selected. The influence of the tungsten matrix element on the analytical signals of analytes and methods for accounting for it have been studied. A comparison of possibilities of using spectroscopic methods for determining Co, Cr, Ti, and V was carried out. It was shown that the ICP-AES method is dominant in determining elements in the concentration range from 1 × 10^–3 to <i>n</i> × 10% in materials based on tungsten carbide.</p>