The relative performance of various metal-incorporated mesoporous silicas of the TUD-1 structure type (M-TUD-1, where M = Ti, Cr, Co, Fe, Cu, Mn) in the selective aerobic oxidation of cyclohexane with tert-butylhydroperoxide and cyclohexylhydroperoxide (CHHP) to the respective hydroperoxides and subsequent decomposition to the alcohol and ketone is reported. In particular, relationships regarding metal type and loading, silica structure type and peroxide initiator are elucidated, to show that it is possible to tune catalysts for either CHHP formation or CHHP decomposition.