Molybdenum blue (MB), is a polyoxometalate with a nanoring structure comprising Mo5+-O-Mo6+ bridges, which is active for the catalytic oxidation of cyclohexane to cyclohexanol and cyclohexanone. However, little is known about the mechanistic features responsible of this catalytic activity. In the present work, the Mo5+-O-Mo6+ moieties embedded in the MB nanoring structure were characterized using diffuse reflectance-UV-Visible spectroscopy and solid state EPR spectroscopy. The amount of Mo5+ centres was then varied by thermal treatment of the polyoxometalate in the absence of oxygen, and the resultant effect on the catalytic activity was investigated. It was observed that, an increased amount of Mo5+ centres preserved the conversion of cyclohexane (ca. 6 %) but led to a loss of selectivity to cyclohexanol giving cyclohexanone as the major product, and the simultaneous formation of adipic acid. To rationalise these results the catalysts were studied using EPR spin trapping to investigate the decomposition of cyclohexyl hydroperoxide (CHHP), a key intermediate in the oxidation process of cyclohexane. This analysis showed that CHHP has to be bound to the MB surface in order to explain its catalytic activity and product distribution. [GRAPHICS] .