Cyclohexanone is an important intermediate for the fabrication of synthetic polymers such as Nylon in chemical industry. A green synthesis of cyclohexanone under mild conditions using environmental friendly oxidants and non-precious catalysts is highly desired. Herein, one-dimensional crystalline h-WO3 nanorods have been synthesized via a facile hydrothermal method. The h-WO3 nanorods are assembled by the closely packed and highly aligned thin nanowires with the lengths up to 10 mu m and diameters of about 10 nm, growing along the [001] direction. The h-WO3 nanorods are used as the catalyst for the first time in the selective oxidation of cyclohexanol to cyclohexanone by aqueous hydrogen peroxide. The effective catalysis by h-WO3 nanorods remarkably increases the yield of cyclohexanone from 3.1 to 78.6 %, under the mild conditions (80 A degrees C, ambient pressure). With a high recyclability, the h-WO3 nanorods have shown great potentials in green chemistry for the synthesis of cyclohexanone by the catalytic oxidation of cylohexanol.