Acrylonitrile and styrene are used as the raw materials for manufacturing acrylic fiber, thus they are often found as pollutants in the petrochemical wastewater. This study utilizes ozone to decompose the organic nitrogen contained in acrylonitrile and styrene, and the oxidation process was monitored using on-line measurements of oxidation-reduction potential (ORP) and pH. The efficiency of organic nitrogen decomposition was also estimated based on the COD, organic nitrogen, TOC, ammonia-N, nitrite, and nitrate measurements. Both the initial pH and alkalinity are observed to affect the degradation rate of organic nitrogen. The acrylonitrile sample with the lowest initial pH value (i.e., 4.0) has a shorter t1/2 of 18.9 min and that for samples of the highest initial pH (i.e., 11) was 34 min. The alkalinity of one acrylonitrile sample was boosted by adding 500 mg/l CaCO3, to simulate the field ABS (Acrylonitrile-Butadiene-Styrene) wastewater effluent. It was observed that within a short ozone contact time, the acrylonitrile sample spiked with 500 mg/l CaCO3 had the highest COD decomposition rate of 0.411 min−1, or 1.3 times more than that for samples without addition of CaCO3. Results of the ozonation process can be fitted with a modified Nernst equation for the various pH conditions. Additionally, the ozone treated synthetic ABS sample shows a faster COD removal rate in the subsequent biological process than those samples without ozone treatment.