Reactive evaporation process was introduced as a simple technique for the fabrication of aligned ZnO nanowires on a Si (100) surface. Single crystalline ZnO nanowire arrays were successfully synthesized on Au coated Si substrates via a VLS growth mechanism. The diameter of ZnO nanowires were observed to vary from 40 nm to 150 nm and the ratio of length to diameter was observed to be larger than 30. The diameter of ZnO nanowires was controlled by changing the processing temperature and by the thickness of Au catalyst film. Green emission induced from singly ionized oxygen vacancies was generated from ZnO nanowires with the excitonic emission in UV range. Higher intensity of the green emission was observed in thinner nanowires, which is attributed to their higher surface-to-volume ratio. Aligned structure formation and size control of ZnO nanowires could provide the potential for various nano-scale device applications.