One-dimensional α- and β-MnO2 single-crystalline nanostructures were prepared by the molten salt route. Both α- and β-MnO2 nanostructures exhibited large aspect ratios with diameters of tens of nanometers and lengths as long as several micrometers. The formation mechanism of α/β-MnO2 nanostructures was proposed on the basis of the time-dependent experiments. In addition, the as-prepared α- and β-MnO2 nanostructures showed excellent catalytic performance in the Fenton-like reaction.