The hydrothermal treatment of molybdenum oxide in alkaline medium leads to micro and nano-fibers products among which bundles to nanofibers with dimensions in the range to 4 -5 µm length and 200 -700 nm wide are found. The microcrystalline product corresponds to a laminar phase with interlaminar spaces smaller than both its intermediate precursor and the pristine MoO 3 . Comparison of the X-ray diffraction patterns and vibrational spectra of the pristine phase, intermediate and final products indicates a mechanism in which tubular species would be formed by the transformation under hydrothermal conditions of an intermediate state produced by a relative displacement of the laminas in the pristine a-MoO 3 .