We report on the self-assembly of core–shell Ge/In–Te nanowires (NWs) on single crystal Si substrates by Metalorganic Chemical Vapour Deposition (MOCVD), coupled to the Vapour–Liquid–Solid (VLS) mechanism, catalysed by Au nanoparticles (NPs). The NWs are formed by a crystalline Ge core and an InTe (II) shell, have diameters down to 15 nm and show oriented growth direction. The role of the MOCVD process parameters and of the NPs size in determining the NWs core–shell microstructure and their alignment was investigated by high-resolution TEM, EDX, XRD and Raman spectroscopy.