Pure phase Zn2GeO4 nanowires (NWs) were grown by the chemical vapor transport method on p-GaN: Mg/Al2O3 substrate. The as-grown Zn2GeO4 NWs exhibited n-type characteristic due to native defects and formed a p-n heterojunction with the p-GaN substrate. The unique energy level of Zn2GeO4 NWs promotes electron injection into GaN active region while suppressing hole injection into Zn2GeO4 NWs. The device exhibited an emission centered at 426 nm and a low turn-on voltage around 4 V. Zn2GeO4 NWs are first reported in this paper as promising electron transport and injection material for electroluminescent devices.