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ZnO microrods were assembled on p-GaN substrate to form a heterostructural light-emitting diode (LED) array. Ultraviolet (UV) emission was obtained under a low forward bias of 3.5 V. The investigation on the electroluminescence, photoluminescence demonstrated three distinct electron-hole recombination processes. The relative intensity of these three emission bands changed with increase of the forward bias, and resulted in blue shift and spectral narrowing of electroluminescence. The present work provides a facile technique for micro-/nano-devices fabrication besides obtaining UV LED arrays.