The role of tunnel K+ ions on the growth and stability of tunnel-structured cryptomelane-type MnO2 nanofibers (denoted as cryptomelane nanofibers hereafter) has been discussed by means of X-ray diffraction and electron microscopy. Cryptomelane nanofibers with typical diameters of 20–80 nm and lengths of 1–6 μm have been synthesized by means of a simple hydrothermal reaction of KMnO4 and MnSO4 aqueous solutions at 140 °C. The growth of cryptomelane nanofibers under hydrothermal conditions follows a dissolution–recrystallization process and involves a morphological transformation from a layered precursor to the tunnel-structured cryptomelane, in which the K+ ions play important roles in templating and…