SnO(2)/Sn nanocables have been grown on single-crystal Si substrates by metal catalyst assisted thermal evaporation of SnO powders. The morphologies and structures of the prepared nanocables were determined on the basis of field emission scanning electron microscopy (FESEM), high-resolution transmission electron microscopy (HRTEM), x-ray diffraction (XRD), Raman and photoluminescence (PL) spectra analyses. The microstructures and compositions of the top and bottom regions of the SnO(2)/Sn nanocables were identified by HRTEM in detail, which revealed some basic physical and chemical processes involved in the formation of the nanocables. A growth model was proposed to address the formation of SnO(2)/Sn nanocables on the basis of the vapour-liquid-solid (VLS) process.