The dicumyl hydroperoxide (DCP) process, based on the condensation of cumene hydroperoxide (CHP) and cumyl alcohol (CA) with DCP, is currently used worldwide for DCP synthesis, which produces large amounts of sulfur-containing wastewater, which is a serious contaminant. In this paper, a new catalytic system (ionic liquid + Na2CO3) for the catalytic oxidation of cumene is proposed. By changing different reaction conditions, cumene is oxidized to a mixture of CHP/ CA approximate to 1:1, and the mixture directly produces DCP by condensation. Compared with the traditional DCP process, the step of CHP reduction is eliminated, which can reduce pollution and have great industrial value. The results showed that when [Bmim]OH + Na2CO3 was used as the catalytic system, the optimum reaction conditions were 90 C, 14 h, 15 g of cumene, 80 mg of [Bmim]OH, 20 mg of Na2CO3, and 120 mL/min of air flow. The selectivity of CHP and CA under these conditions were 45.77 and 43.21%, respectively.