In this study, post-treatment of bio-treated acrylonitrile wastewater was performed using the UV/Fenton process. Five target compounds (furmaronitrile, 3-pyridinecarbonitrile, 1,3-dicyanobenzene, 5-methyl-1H-benzotriazole, and 7-azaindole) were selected as target compounds and their degradation kinetics were examined. Under optimal reaction conditions (HO dosage 3.0 mM, Fe dosage 0.3 mM, and initial pH 3.0), more than 85% of total organic carbon (TOC) was eliminated in 30 min when a 10-W UV lamp was employed, and the electrical energy per order of magnitude for TOC removal was as low as 2.96 kWh m. Furthermore, the target compounds and the toxicity were largely removed from the bio-treated effluent. Size exclusion chromatography with organic carbon detector analysis revealed that organic components with a wide range of molecular weights were greatly reduced after the UV/Fenton process. A simplified pseudo steady-state (SPSS) model was applied to predict the degradation of target compounds during the UV/Fenton process. The concentrations of generated hydroxyl radicals were estimated to be 3.06 × 10 M, 6.37 × 10 M, and 10.9 × 10 M under 5-, 10-, and 15-W UV lamps, respectively. These results demonstrate that the proposed SPSS model fitted well with experimental data on the post-treatment of real wastewater, and consequently indicate that this model can be a useful tool in the prediction of degradation of target compounds during the UV/Fenton process.