In this work, thin films of Bi2Te3 and Sb2Te3 were synthesized by the nanoalloying approach: Nanoscale layers of the elements Element nanoscale layers of Bi, Sb and Te are stoichiometrically deposited on a cold substrate using a MBE setup and subjected to an annealing process in which a solid state reaction yielding Bi2Te3 and Sb2Te3 takes place. Besides the two binary compounds, nanoscale multilayer (ML) stacks of 9 nm Bi2Te3/9 nm Sb2Te3 were created. The electrical transport properties of the binary compounds were determined in dependence of composition. Compound formation was directly observed in temperature-dependent in-situ XRD scans and was found to start at ∼100 °C. The stability of the Bi2Te3/Sb2Te3 ML nanostructure against temperature-driven interdiffusion during annealing was examined by SIMS and TEM for an annealing temperature of 150 and 250 °C, respectively. A comparative TEM study of the as grown and annealed state is presented.