A radio frequency (RF) plasma system used to decompose trifluoromethane (CHF 3 or HFC-23) is demonstrated. The CHF 3 decomposition fractions (η CHF 3 ) and mole fractions of detected products in the effluent gas streams of CHF 3 /O 2 /Ar and CHF 3 /H 2 /Ar plasma systems, respectively, have been determined. The effects of four experimental parameters, input power, O 2 /CHF 3 or H 2 / CHF 3 ratio, operational pressure, and the CHF 3 feeding concentration were investigated. The same species detected in the effluent gas streams of both CHF 3 /O 2 /Ar and CHF 3 /H 2 /Ar plasma systems were CH 2 F 2 , CF 4 , HF, and SiF 4 . However, the CO 2 and COF 2 were detected only in the CHF 3 /O 2 /Ar plasma system and the CH 4 , C 2 H 2 , and CH 3 F were detected only in the CHF 3 /H 2 / Ar plasma system. The results of a model sensitivity analysis showed that the input power was the most influential parameter for η CHF 3 both in the CHF 3 /O 2 /Ar and CHF 3 /H 2 /Ar plasma systems. Furthermore, the possible reaction pathways were built up and elucidated in this study. The addition of hydrogen for CHF 3 decomposition can produce a significant amount of HF and the main carbonaceous byproducts were CH 4 and C 2 H 2 . Even though the η CHF 3 in the CHF 3 /H 2 /Ar plasma system is lower than that in the CHF 3 /O 2 /Ar plasma system, but due to the more advantages mentioned above, a hydrogen-based RF plasma system is a better alternative to decompose CHF 3 .