The aim of the present study was the synthesis and characterization of WO3 and WS2 nanostructures in hexagonal phases and the evaluation of the latter as catalyst in the dibenzothiophene hydrodesulfurization reaction. 2H-WS2 nanostructures were obtained from a precursor WO3 nanostructure by a two-step hydrothermal/gas phase reaction under well-controlled conditions. All nanostructures were characterized by X-ray powder diffraction, scanning electron microscopy, transmission electron microscopy, and the specific surface area of the materials was measured using the BET method. The catalytic activity and selectivity measurements of the resulting unsupported WS2 nanocatalysts are also presented. Catalytic activity was found to be highest for the 2H-WS2 from the WO3 nanostructure sulfided at 773 K (rate constant of 3 x 10(-7) mol/g s).