The axial Zn 2 GeO 4 /ZnO nanowire heterojunction was successfully synthesized via chemical vapor deposition (CVD) approach. The transmission electron microscopy (TEM) study revealed that the growth follows the vapor–liquid–solid (VLS) mechanism with an orientation relationship of (300) Zn2GeO4 //(−110) ZnO and (003) Zn2GeO4 //(110) ZnO , in which a small lattice mismatch between Zn 2 GeO 4 and ZnO was observed. The ZnO segment grows out axially along Zn 2 GeO 4 ternary nanowire and its length can be tuned from tens of nanometers to over 10μm by adjusting the ZnO source supply. This ternary/binary nanowire heterojunction shows a diode effect via nano-manipulators in-situ measurement under field emission scanning electron microsocpy (FESEM).