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This study investigates the application of a radio-frequency-powered plasma with a Pt/γ-Al2O3 catalyst to decompose the chlorinated volatile organic compound of vinyl chloride (VC) in air. The use of an atmospheric-pressure plasma jet is explored as an innovative technology for the treatment of VC. The effects of some major system parameters such as input power (PWI), plasma energy density, initial concentration of VC (C0), and space velocity (SV) of the catalyst on the plateau temperature (TP) of a reactor and conversions of VC (XVC) are studied and elucidated. The results show that the effectiveness of the plasma-assisted catalysis is evident as indicated by the increase of XVC and the rate constant. At a PWI of 250 W without a catalyst, the values of XVC were 14% and 5.4% for C0 = 200 and 450 ppmv, respectively. In the presence of the Pt/γ-Al2O3 catalyst with an SV of 17 400 h-1, the values of XVC for C0 = 200 and 450 ppmv increased to 49% and 39%, respectively. Note that the values of TP were 550 K and 430 K without and with the Pt/γ-Al2O3 catalyst at an SV of 17 400 h-1 and a PWI of 250 W. The proposed kinetic models describe the relationships of C/C0 with the major parameters for the plasma and plasma-assisted catalytic degradation of VC, showing good agreement with the experimental data. The information obtained is useful for the operation, design, and analysis of plasma devices.