We report an aqueous chemical method to fabricate well-aligned ZnO/Al(2)O(3) nanocrystal (NC) core-shell nanorod arrays (NRAs). Structural characterization showed that the shell layers are composed of alpha-Al(2)O(3) nanocrystals. Photoluminescence measurements showed the enhancement of near-band-edge (NBE) emission of ZnO NRAs due to the presence of Al(2)O(3) NC shells. The Al(2)O(3) NC shell layer resulting in the flat-band effect near the ZnO surface leads to a stronger overlap of the wavefunctions of electrons and holes in the ZnO core, further enhancing the NBE emission. This approach should be very useful in designing many other core-shell NRAs for creating varieties of high-efficiency optoelectronic devices.