ZnO nanowires have been grown on sapphire and Si substrates using catalytic growth. A strong near-band-gap ultraviolet emission is observed at room temperature. By carefully studying the temperature dependence of ZnO wire emission, we found that the room-temperature UV emission contains two different transitions; one is related to the ZnO free exciton and the other is related to the free-to-bound transition. The bound state has a binding energy of about 124 meV. The results from optical measurements show that a high quality of ZnO nanowires grown on sapphire and Si substrates has been achieved.