We describe a simple method to assemble ZnO nanowires/belts into highly ordered arrays. ZnCu2 alloy was used as the Zn source, which reacted with water vapor to generate ZnO nanocrystals. The reaction was performed in a mild way, which facilitated the easy control of the reaction conditions. By simply controlling the water bath temperature and carrier gas flux in our experiments, we obtained ZnO nanowires/belts aligned to form ordered arrays. The highly ordered nature of the ZnO arrays is suggested to be related both with the polarities of the H2O molecule and the ZnO (0001) surface. Photoluminescence (PL) microscopy revealed that the comblike structures had waveguide properties, where green light enhancement was observed at the tips of the branches. The light enhancement property reveals their promising applications as light source arrays.