Understanding size/dimensionality-dependent phenomena and processes relevant to chemical sensing and catalysis requires analytical methods with high surface sensitivity, which can exploit the structure and composition of nanomaterials at their natural length scales and working conditions. In the present study, we explored the potentials and complementary capabilities of several surface-sensitive microscopy approaches to shed light on the properties of individual SnO(2) nanowires and their networks. Our results demonstrate the unique opportunities provided by synchrotron-based photoelectron microscopies for surface-sensitive structural and chemical analysis, including in situ characterization of electron transport properties of a nanostructure wired as an active element in chemiresistor devices.