Nanostructured MnWO4 catalysts prepared with different initial pH exhibited systematic variation in the activity in the selective oxidation of cyclohexane. 2-propanol TPD showed that the ratio of Mn to W related sites increased with the initial synthesis pH. W sites were found to be mainly active in the formation of CHHP and dehydrogenation of cyclohexanol, while Mn sites appeared to be more active in decomposition of CHHP and deep oxidation, giving a significant selectivity to adipic acid. The high yield of KA oil at intermediate synthesis pH suggests an optimum balance of Mn and W surface sites.