The novel hexaniobate nanotubes with variable interlayer spacings have been prepared via intercalating-exfoliating-rolling mechanism at the room temperature. The hexaniobate nanotubes are single crystalline with multiple walls. A few single-wall nanotubes have been observed also. The interlayer spacings of 0.83, 1.9, 2.2, 2.3, 2.4, 2.5, 2.8, 3.3 and 3.6 nm are, respectively, obtained by the intercalation of a series of primary alkylamines. The formation mechanism is discussed in detail and this method is applicable to other layered structure materials. These hexaniobate nanotubes are inorganic/organic composite and therefore represent a new class of tubular materials. (C) 2004 Elsevier B.V. All rights reserved.