Selective oxidation of 4-tert-butyltoluene (TBT) to 4-tert-butylbenzaldehyde (TBBZ) and 4-methylacetophenone (MAP) is reported for the first time using aqueous hydrogen peroxide as oxidant and Co/MCM-41 as the catalyst under mild conditions for the first time. Co/MCM-41 presented reasonable selectivity (82%) of TBBZ with a conversion rate of 15% of TBT without any initiator. Under the suitable reaction conditions, Co/MCM-41 also presented reasonable selectivity (58%) of MAP with a conversion rate of 12% of the substrate. The catalysts can be reused once with almost the same activity.