The synthesis, characterization, experimental X-ray photoelectron spectra (XPS) and density-functional theory (DFT) investigations on solid solutions of Mo1-xRexS2 (x = 0.05, 0.10, 0.15 and 0.20) are reported herein. It is shown that even at a low concentration of dopant Re atoms, clustering occurs. At an Re concentration of 5% the formation of dimer-like impregnations is observed. An increase in the dopant concentration leads to an increase in the amount of clustered rhenium atoms and to the formation of rhombic clusters. The absence of magnetism within the studied Mo1-xRexS2 solid solutions allowed us to suggest a mechanism for the distribution of rhenium inside molybdenum disulphide through the initial formation of rhenium disulphide and its subsequent spreading.