Pyridinium dichromate, chromium trioxide and CrAlPO-5 showed a very similar selectivity pattern in the decomposition of cyclohexyl hydroperoxide. CrAPO-5 turned out to be a real heterogeneous catalyst, most likely acting via a similar mechanism to the homogeneous catalysts. Molecular modeling indicates that heterolytic decomposition of the intermediate cyclohexyl peroxychromate ester yields cyclohexanone and H2CrO4 via a cyclic transition state.