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Knowing and controlling the resistivity of an individual nanowire (NW) is crucial for the production of new sensors and devices. For ZnO NWs this is poorly understood; a 10(8) variation in resistivity has previously been reported, making the production of reproducible devices almost impossible. Here, we provide accurate resistivity measurements of individual NWs, using a four-probe scanning tunnelling microscope (STM), revealing a dependence on the NW dimensions. To correctly interpret this behaviour, an atomic level transmission electron microscopy technique was employed to study the structural properties of the NWs in relation to three growth techniques: hydrothermal, catalytic and non-catalytic vapour phase. All NWs were found to be defect free and structurally equivalent; those grown with a metallic catalyst were free from Au contamination. The resistivity measurements showed a distinct increase with decreasing NW diameter, independent of growth technique. The increasing resistivity at small NW diameters was attributed to the dominance of surface states removing electrons from the bulk. However, a fundamental variance in resistivity (10(2)) was observed and attributed to changes in occupied surface state density, an effect which is not seen with other NW materials such as Si. This is examined by a model to predict the effect of surface state occupancy on the measured resistivity and is confirmed with measurements after passivating the ZnO surface. Our results provide an understanding of the primary influence of the reactive nature of the surface and its dramatic effect on the electrical properties of ZnO NWs.