Wire-like micro- and nanocrystals of SnO₂ are obtained via gas-transport synthesis. The specifics of the atomic and electronic structure of an array of SnO₂ wire-like crystals is revealed using near-edge X-ray absorption and X-ray photoelectron spectra. The method of photoemission electron microscopy with high-intensity synchrotron (undulator) radiation is used to study the morphology of SnO₂ wire-like crystals for the first time.