Purpose: of this paper is to study the structure of melts of quasi-binary system Bi2Te3-PbTe by means of X-ray diffraction method. The aim of the research was to investigate the short range order in melts comparing it with the structure in solid state. Design/methodology/approach: Analysis of the structural factors, radial distribution functions of atoms and basic structural parameters showed that the structure of melts at temperatures near the liquidus shows microheterogeneity. Findings: On the basis of the analysis of structural factors, functions of the radial distribution of atoms and basic structural parameters, it is shown that in the given concentration the short range order structure of liquid alloys of pseudo-binary PbTe-Bi2Te3 system is microinhomogeneous and is characterized by the presence of associates, whose atomic arrangement is like to the structure of solid compounds, existing in this concentration range. Research limitations/implications: To complete the understanding of short-range order effect on the formation of the physical properties of Pb-Bi-Te alloys, further studies of the thermoelectric properties of these alloys in the liquid state are needed. Practical implications: The promise of the considered direction requires an experimental and theoretical study of the processes of bulk, thin film and nanostructured material. In this case, it is necessary to develop a technology for the synthesis of compounds of Pb-Bi-Te system, obtaining thin films and nanostructures using the vapour phase methods with studying the mechanisms of thermoelectric properties of the material formation and optimization of technological regimes for obtaining effective thermoelectric materials based on compounds of Pb-Te-Bi system. Originality/value: The processes of structure formation of nanosystems with given characteristics are investigated, because among numerous thermoelectric materials, bismuth telluride (Bi2Te3) and its alloys are the most important thermoelectric materials used in state-of-the-art devices near room temperature, and lead telluride (PbTe)-based alloys are extensively used in power supplies for space exploration and generators for use at medium to high temperatures.