Single-crystal SnO2 nanofibers have been formed from SnO2 polycrystals via reaction at low oxygen partial pressures. Polycrystalline SnO2 disks coated with Au nanoparticles were exposed to humid H2/N2 at 700 to 800 °C. Single-crystal SnO2 nanofibers formed beneath Au nanoparticles, with the nanofiber length oriented parallel to the [100] crystallographic direction of SnO2. Because this simple process does not require either a separate source of a Sn–O-bearing vapor species located upstream of the substrate or a temperature gradient, single-crystal nanofibers may be formed on large area SnO2-bearing substrates.