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CdS/SiO2 nanowire arrays and CdS nanobelts were synthesized by thermal evaporation of CdS and CdO mixture powders, with highly selective etching occurring on the silicon substrate surfaces. Study of the growth mechanism of CdS/SiO2 nanowire arrays and the growth process of CdS nanobelts showed that the growth of CdS dendrites plays an important role in the formation of CdS/SiO2 nanowire arrays, and that the mechanism ofCdS/SiO2 nanowire arrays growth was in good agreement with"self-assembling nanoelectrochemistry". In the thermal evaporation process, an interaction between Si from silicon substrate and Cd took place.