High-quality Mn:ZnO (MZO) film had been prepared on N-GaN coated sapphire substrates followed by postdeposition thermal annealing treatment at 700 °C. For the annealed MZO/GaN heterojunction, a 15 nm cubic structural ZnGa(2)O(4) layer was observed at the MZO/GaN interface through transmission electron microscope analysis. Through electroluminescence (EL) measurement, the formation of the nanointerface results in an EL transition from ultraviolet- to red-dominant mode for n-Mn:ZnO/N-GaN heterojunction light-emitting diodes (LEDs). The heterojunction LED showed a rectification ratio of ∼2.0 × 10(5) at ±2 V, a dark current of 3.5 nA at -2 V and a quite strong red EL with a low turn-on voltage of 3 V. On the basis of the energy band diagram, we think the EL transition from ultraviolet- to red-dominant mode is mainly due to the formation of a thin oxide blocking nanolayer at the MZO/GaN interface during the annealing process.