As an important II-VI semiconductor, ZnO has attracted increasing interests owing to its unique properties such as wide band-gap (3.37 eV) and large exciton binding energy (60 meV).[1] ZnO has shown great potential in optoelectronic devices such as light emitting diodes (LED) and laser diodes (LDs) operating in the short-wavelength or UV region.[2]Compared to their thin-film counterparts, [3][4] nanoscale devices assembled on free-standing nanowires [5][6][7][8][9][10] could enable new functions, high efficiency, enhanced performance, and diverse applications. [11][12][13][14][15][16][17][18][19][20] As in thin-film devices, the success of nanodevices similarly relies on the capability of controlling the transport and electrical properties of the selected materials. Doping via introducing electron donor or acceptor elements into the host crystal is a successful approach in thin-film or planar electronic/optoelectronic devices. However, such doping approach remains a challenge for nanostructured materials. To date, while n-and p-type dopings have been achieved in Si, [11][12] InP, [13] CdS, [14] and GaN [15] nanowires/ nanoribbons, many issues of doping, such as control of doping type and conductivity, remain largely untapped or unresolved. For ZnO nanostructures, group III elements (Al, Ga, or In) are commonly used to substitute Zn to induce n-type conductivity. The success of doping is often accompanied and characterized by changes in optical, electrical, and/or structural properties of ZnO nanostructures. For example, Al-doped ZnO nanowires exhibited a blue shift from 3.29 to 3.34 eV in the cathodoluminescent (CL) spectra.[21] Ga 2 O 3 was also employed to dope n-type ZnO nanofibers grown in a vaporphase transport process. [22] however switched to n-type after two months storage in an ambient environment. Despite the considerable efforts, rational synthesis of ZnO nanostructures with tunable n-type conductivity is not available. The as-synthesized ZnO nanostructures are often randomly oriented, and thus have limited applications in optoelectronic devices. Therefore, it is necessary to have a better understanding of the doping efficiency and transport properties of ZnO nanostructures. Herein, we report a controlled growth and doping process of well-aligned ZnO nanowire (NW) arrays via thermal evaporation. The growth direction of ZnO NWs was found to depend on the dopant content, and NW conductivity could be varied over two orders of magnitude. The electrical properties of ZnO NWs were characterized using single-nanowire field-effect transistors (FETs). Figure 1 shows the electron microscopy images of ZnO NW arrays synthesized on a-plane sapphire substrates. The content of Ga 2 O 3 in the source mixtures was varied from 0 to 1 at %. The representative NWs synthesized with 0, 0.2, and 1 at % of Ga 2 O 3 are denoted as samples A, B, and C, respectively. Both the undoped (Fig. 1a and b) and Ga-doped (Fig. 1c) ZnO NWs are aligned vertically on the substrates, and uniform over a large area. The NWs have a uniform dia...