Four quaternary ammonium salts were synthesized from TMEDA and DABCO,and their structures were characterized by elemental analysis and1H NMR. Then they were used as co-catalyst with NHPI in the catalytic oxidation of ethylbenzene. Our experiments showed that 84. 5% conversion of ethylbenzene and 88. 1% selectivity of acetophenone could be obtained under the following conditions: 80 ℃,0. 3 MPa of oxygen pressure and 7 h reaction time.